Supramolecular assemblies between macrocyclic porphyrin hexamers and star-shaped porphyrin arrays

Article abstract of DOI:10.1021/jo0015523

The syntheses of eight new star-shaped D3-symmetric arrays in which three 15-(pyrid-4-yl)porphyrin subunits are attached to the 1, 3, and 5 positions of a benzene core through linkers consisting of collinear repetitive phenylethynyl units have been carried out using Pd(O)-catalyzed coupling reactions. By the same procedure, an analogous 10-(4-pyridin-yl)porphyrin hexamer in which all positions of the benzene core are substitued has been obtained. Likewise, the preparation of suitably sized cyclic porphyrin hexamers, in which all six or at least three alternate porphyrin rings are complexed with Zn(II) ions, is described in detail. In solution, such cyclic porphyrin hexamers form supramolecular assemblies with the star-shaped polyporphyrins in which the latter are held in the interior of the macrocycle through coordination of the apical pyridine rings with the Zn(II) ions. The suggested structures are supported by ¹H NMR spectroscopic and MALDI-TOF mass spectrometric measurements. They agree with the high values of the binding constants of the corresponding supramolecules, which range between K = 1.1 × 10¹⁰ and 1.4 × 10⁹ M-1.

Full text of DOI:10.1021/jo0015523

J . Org. Chem. 2001, 66, 4973-4988
4973
Su p r a m olecu la r Assem blies betw een Ma cr ocyclic P or p h yr in
†
Hexa m er s a n d Sta r -Sh a p ed P or p h yr in Ar r a ys
Simona Rucareanu, Olivier Mongin, Anne Schuwey, Nicolas Hoyler, and Albert Gossauer*
Institut f u¨ r Organische Chemie der Universit a¨ t, Ch. du Mus e´ e 9, CH-1700 Fribourg, Switzerland
Walter Amrein and Hans-Ulrich Hediger
Laboratorium f u¨ r Organische Chemie, ETH-Zentrum, Universit a¨ tsstrasse 16,
CH-8092 Z u¨ rich, Switzerland
albert.gossauer@unifr.ch
Received November 2, 2000
3
The syntheses of eight new star-shaped D -symmetric arrays in which three 15-(pyrid-4-yl)porphyrin
subunits are attached to the 1, 3, and 5 positions of a benzene core through linkers consisting of
collinear repetitive phenylethynyl units have been carried out using Pd(0)-catalyzed coupling
reactions. By the same procedure, an analogous 10-(4-pyridin-yl)porphyrin hexamer in which all
positions of the benzene core are substitued has been obtained. Likewise, the preparation of suitably
sized cyclic porphyrin hexamers, in which all six or at least three alternate porphyrin rings are
complexed with Zn(II) ions, is described in detail. In solution, such cyclic porphyrin hexamers form
supramolecular assemblies with the star-shaped polyporphyrins in which the latter are held in
the interior of the macrocycle through coordination of the apical pyridine rings with the Zn(II)
1
ions. The suggested structures are supported by H NMR spectroscopic and MALDI-TOF mass
spectrometric measurements. They agree with the high values of the binding constants of the
1
0
9
-1
corresponding supramolecules, which range between K ) 1.1 × 10 and 1.4 ×10 M
.
In tr od u ction
phyrin arrays could be accessible, in which the star-
shaped polyporphyrins would be located inside the cavity
of the doughnut-shaped porphyrin hexamer. For this
purpose, however, the “guest” molecules had to be modi-
fied in order to ensure an intermolecular noncovalent
bonding with the macrocyclic hexamer as the “host”.
Thus, the present work deals with the syntheses of eight
new benzene-centered porphyrin trimers (18, 19a -f, and
The study of intermolecular bonding, for which the
term supramolecular chemistry was coined by Lehn in
988, has evolved in the past decade to a new, rapidly
expanding research field, in which the future develop-
1
1
2
3
ment of enzyme-mimetic catalysts, optical switches,
4
5
molecular photonic wires, light-harvesting arrays, mo-
6
lecular devices, and a wealth of further practical ap-
plications is rooted. In a recent paper, we reported the
2
0) and a porphyrin hexamer (23), all of them bearing
7
pyridine rings instead of benzene rings at the apical
positions. As, in general, replacement of pyrid-4-yl for
phenyl at the apical positions brought about a loss of
solubility of the porphyrin trimers, the introduction of
alkyl chains instead of phenyl substituents at the vicinal
meso C-atoms of the porphine rings proved to be advan-
tageous for the purpose of the work. On the other hand,
the syntheses of five macrocyclic porphyrin hexamers
synthesis of a macrocyclic porphyrin hexamer surround-
ing a cavity with a diameter of about 4.6 nm (Figure 1).
As this value closely corresponds to the size of some star-
8
shaped porphyrin trimers and a porphyrin hexamer
9
(
niphaphyrin) which have been synthesized also in our
laboratory, it became obvious to investigate whether
supramolecular assemblies between both kinds of por-
*
To whom correspondence should be addressed. Phone: 41-26-300
8
770. Fax: (int) +41-26 300 9739.
(5) Wennerstr o¨ m, O.; Ericsson, H.; Raston, I.; Svensson, S.; Pimlott,
W. Tetrahedron Lett. 1989, 30, 1129-1132. Prathapan, S.; J ohnson,
T. E.; Lindsey, J . S. J . Am. Chem. Soc. 1993, 115, 7519-7520. Seth,
J .; Palaniappan, V.; J ohnson, T. E.; Prathapan, S.; Lindsey, J . S.;
Bocian, D. F. J . Am. Chem. Soc. 1994, 116, 10578-10592. Wagner, R.
W.; J ohnson, T. E.; Li, F.; Lindsey, J . S. J . Org. Chem. 1995, 60, 5266-
5273. Wagner, R. W.; J ohnson, T. E.; Lindsey, J . S. J . Am. Chem. Soc.
1996, 118, 11166-11180. Hsiao, J .-S.; Krueger, B. P.; Wagner, R. W.;
J ohnson, T. E.; Delaney, J . K.; Mauzerall, D. C.; Fleming, G. R.;
Lindsey, J . S.; Bocian, D. F.; Donohoe, R. J . J . Am. Chem. Soc. 1996,
118, 11181-11193. Seth, J .; Palaniappan, V.; Wagner, R. W.; J ohnson,
T. E.; Lindsey, J . S.; Bocian, D. F. J . Am. Chem. Soc. 1996, 118, 11194-
11207. Gauler, R.; Risch, N. Tetrahedron Lett. 1997, 38, 223-224.
(6) Wagner, R. W.; Lindsey, J . S.; Seth, J .; Palaniappan, V.; Bocian,
D. F. J . Am. Chem. Soc. 1996, 118, 3996-3997.
†
Dedicated to Prof. Dr. Richard Neidlein (Pharmazeutisch-Chemis-
ches Institut der Ruprecht-Karls-Universit a¨ t Heidelberg) on the oc-
casion of his 70th birthday.
(
1) Lehn, J .-M. Angew. Chem. 1988, 100, 92-116; Angew. Chem.,
Int. Ed. Engl. 1988, 27, 89.
2) Milgrom, L. R. J . Chem. Soc., Perkin Trans. 1 1983, 2535-2538.
Davila, J .; Harriman, A.; Milgrom, L. R. Chem. Phys. Lett. 1987, 136,
27-430; Anderson, H. L.; Anderson, S.; Sanders, J . K. M. J . Chem.
(
4
Soc., Chem. Commun. 1989, 1714-1715. Bonnett, R.; Ioannou S.;
Pearson, C.; Petty, M. C.; Roger-Evans, M.; Wilkins, R. F. J . Mater.
Chem. 1995, 5, 237-242. Anderson, H. L.; Sanders, J . K. M. J . Chem.
Soc., Perkin Trans. 1 1995, 2223-2229. Clyde-Watson, Z.; Bampos,
N.; Sanders, J . K. M. New J . Chem. 1998, 1135-1138.
(
3) O’Neil, M. P.; Niemczyk, M. P.; Svec, W. A.; Gosztola, D.; Gaines
G. L., III.; Wasielewski, M. R. Science 1992, 257, 63-65.
4) Crossley, M. J .; Burn, P. L. J . Chem. Soc., Chem. Commun. 1991,
(7) Mongin, O.; Schuwey, A.; Vallot, M.-A.; Gossauer, A. Tetrahedron
Lett. 1999, 40, 8347-8350.
(
1
9
569-1571. Wagner, RW.; Lindsey, J . S. J . Am. Chem. Soc. 1994, 116,
(8) Mongin, O.; Papamica e¨ l, C.; Hoyler, N.; Gossauer, A. J . Org.
Chem. 1998, 63, 5568-5580.
(9) Mongin, O.; Hoyler, N.; Gossauer, A. Eur. J . Org. Chem. 2000,
1193-1197.
759-9760. Sessler, J . L.; Capuano, V. L.; Harriman, A. J . Am. Chem.
Soc. 1993, 115, 4618-4628. Ono, N.; Tomita, H.; Maruyama, K. J .
Chem. Soc., Perkin Trans. 1 1992, 2453-2456.
1
0.1021/jo0015523 CCC: $20.00 © 2001 American Chemical Society
Published on Web 06/27/2001

4
974 J . Org. Chem., Vol. 66, No. 15, 2001
Rucareanu et al.
F igu r e 1. Toroid-like hexaporphyrin array with different metalated states and an internal diameter of the cavity amounting to
ca. 4.6 nm.
(
1a -e), similar to those described in a preliminary
Reaction of 2b and 2c with 1 equiv of 3 using pal-
ladium(0) as a catalyst gave 4a and 4c, respectively. The
latter were reacted with trimethylsilylacetylene under
palladium(II)-catalyzed conditions to afford 4b and 4d ,
in which two positions (i.e., a protected ethynyl group
and a diethyltriazene-substituted phenyl C-atom) may
be activated selectively. The used divergent/convergent
7
paper, are described in detail in the Experimental
Section. Moreover, the formation of supramolecular
complexes of two porphyrin hexamers (1a and 1d ) with
seven selected porphyrin trimers and the niphaphyrin
2
3 has been demonstrated by measurement of the cor-
1
responding binding constants as well as by H NMR and
mass spectrometry. A similar, but substantially smaller,
supramolecular polyporphyrin array has been synthe-
sized some years ago by Sanders et al.,10 with a different
purpose.
strategy has been described previously for the synthesis
of oligomers of phenylacetylene.1
2,13
Thus, the iodo de-
rivatives 5a and 5c were readily synthesized from 4b and
4d by treatment with methyl iodide, whereas treatment
of 4b with NaOH afforded the deprotected acetylene
derivative 6. Demetalation of 5a with TFA, on the other
hand, led to 5b. Cross-coupling of 5a -c with 6 in the
Resu lts
Syn th esis of Ma cr ocyclic P or p h yr in Hexa m er s
3 4
presence of Pd(PPh ) yielded a set of three porphyrin
(
(
Sch em e 1). Five macrocyclic porphyrin hexamers
1a -e) have been prepared from two building blocks,
dimers (7a -c), which differ only on their metalation state
but contain at their ends the same functional groups as
porphyrins 4b,d .
1
1
namely a diiodoporphyrin derivative (2a ) (as well as its
metal chelates 2b and 2c), and the cornerstone molecule
3
8
The above three-step sequence was then repeated to
prepare the porphyrin tetramers 10a , 10c, and 10e,
which were transformed by reaction with methyl iodide
into 10b, 10d , and 10f, respectively. Thereon, the linear
porphyrin hexamers 11a ,c,e,g were obtained by reaction
of tetramers 10b,d ,f with dimers 9a -c. After subsequent
activation of both terminal functional groups, the four
hexamers were finally cyclized in the presence of pal-
, which was obtained in 87% yield by treatment of the
1
2
corresponding trimethylsilyl derivative with TBAF.
(
10) (a) Anderson, S.; Anderson, H. L.; and Sanders, J . K. M. Angew.
Chem. 1992, 104, 921-924; Angew. Chem., Int. Ed. Engl. 1992, 31,
07. (b) Anderson, S.; Anderson, H. L.; and Sanders, J . Chem. Soc.,
9
Perkin Trans. 1 1995, 2231-2245. (c) Anderson, H. L.; Walter, C. J .;
Vidal-Ferran, A.; Hay, R. A.; Lowden, P. A. and Sanders, J . K. M. J .
Chem. Soc., Perkin Trans. 1 1995, 2275-2279.
(
(
11) Lee, C.-H.; Lindsey, J . S. Tetrahedron 1994, 50, 11427-11440.
12) Zhang, J .; Pesak, D. J .; Ludwick, J . L.; Moore, J . S. J . Am.
(13) Schumm, J . S.; Pearson, D. L.; Tour, J . M. Angew. Chem., Int.
Ed. Engl. 1994, 33, 1360-1363.
Chem. Soc. 1994, 116, 4227-4239.

Supramolecular Assemblies
J . Org. Chem., Vol. 66, No. 15, 2001 4975
Sch em e 1a
a
Reagents and conditions: (a) Ni(OAc)2, 4H2O, CHCl3/AcOH, reflux, 48 h; (b) Pd2dba3, AsPh3, DMF/Et3N, 45 °C, 3 h; (c) Pd(PPh3)4,
DMF/Et3N, 40 °C, 14 h; (d) HCtCSiMe3, Pd(PPh3)2Cl2, CuI, DMF/Et3N, 35 °C, 14 h; (e) CH3I, 135 °C, 2 h; (f) 1 M NaOH, THF, 20 °C; (g)
-
4
-3
TFA, CHCl3, 20 °C; (h) substrate (2.5 × 10 M), Pd(PPh3)4 (1.25 × 10 M), DMF/Et3N, 40 °C, 14 h.
ladium(0) in high-diluted solution, yielding 1a-d (Scheme
). The step-by-step method developed in this work
enables the preparation of cyclic hexamers with different
metalation states such as 1c. Finally, a fifth macrocyclic
hexamer (1e) was obtained by selective demetalation of
with pyrrole in CH
2
Cl
2
, using BF
3
2
‚OEt as a catalyst, was
1
synthesized in order to improve the solubility of the star-
shaped porphyrin trimers and their supramolecular
complexes.
Attempts to prepare 10,20-dialkyl-5-(4-iodophenyl)-15-
(pyrid-4-yl)porphines 14a -e failed using procedures
described in the literature for the preparation of meso-
1
d with TFA.
Syn th esis of Sta r -Sh a p ed P or p h yr in Tr im er s. The
aryl-,1 meso-alkyl-, or meso-pyridylporphyrins.
1,15
14
16,17
On
synthetic route to prepare stellular D
3
-symmetric por-
phyrin trimers 18-20 is given in Scheme 2. The porphy-
rin trimers 19a -f (with a diameter of 4.2 nm) were
designed to accommodate the toroid-shaped macrocycles
the contrary, mixed condensation of dipyrrylmethanes
12a -e with 4-iodobenzaldehyde and 4-pyridinecarbox-
3
aldehyde in CHCl /EtOH, in the presence of TFA, fol-
1
a -e, the internal diameter of which amounts to 4.6 nm.
lowed by oxidation with DDQ, afforded in 10-13% overall
yield the expected mixture of three porphyrins, namely
5,15-dialkyl-10,20-bis(4-iodophenyl)porphine (1-3%), 5,-
15-dialkyl-10,20-bis(pyrid-4-yl)porphine (4-6%), and the
desired porphyrin 14 (3-6%), which were easily sepa-
rated by chromatography. Under the same conditions,
porphyrin 13 was obtained in 12% yield using trimeth-
The diameter of molecules 18 and 20 is smaller (3.3 nm)
and larger (6.9 nm), respectively, than that of trimers
1
9a -f.
meso-Phenyldipyrrylmethane (12f) was prepared ac-
cording to a described procedure.11 A series of meso-
alkyldipyrrylmethanes 12a -e, which were obtained in
3
1
4
2-40% yield as described for the n-pentyl homologue
by condensation of the corresponding alkyl aldehydes
(15) Nagata, T. Bull. Chem. Soc. J pn 1991, 64, 3005-3016.
(16) Roeterdink, F.; van der Plas, H. C. J . Heterocycl. Chem. 1990,
2
7, 1733-1735.
(14) Hammel, D.; Erk, P.; Schuler, B.; Heinze, J .; M u¨ llen, K. Adv.
(17) Anderson, H. L.; Hunter, C. A.; Meah, N. M.; Sanders, J . K. M.
Mater. 1992, 4, 737-739.
J . Am. Chem. Soc. 1990, 112, 5780-5789.

4
976 J . Org. Chem., Vol. 66, No. 15, 2001
Rucareanu et al.
Sch em e 2a
a
Reagents and conditions: (a) BF3‚OEt2, CH2Cl2, 20 °C, 3 h; (b) TFA, CHCl3/EtOH, 20 °C; (c) DDQ, 20 °C, 2 h; (d) Pd(PPh3)4, K2CO3,
MeOH, THF/piperidine, 70 °C, 23 h; (e) Pd2dba3, AsPh3, DMF/Et3N, 35 °C.
ylsilypropynal18 instead of 4-iodobenzaldehyde. The pres-
ence of 5% ethanol in the reaction mixture seems to be
critical, as with a lower content the yield of porphyrins
decreases, whereas the presence of more than 5% ethanol
improves the yield but favors the formation of byproducts
as a consequence of scrambling reactions. The same is
true for the concentration of TFA. The synthesis of 5,-
9-10% yield. This might be due to their lower solubility,
since the yield could be improved to 20% using toluene
instead of DMF as a solvent.
Syn th esis of th e Sta r -Sh a p ed P or p h yr in Hex-
a m er (Nip h a p h yr in ) 23. Reaction of [(2,4,6-triethynyl-
1,3,5-ben zen et r iyl)t r i-2,1-et h yn ediyl]t r is(t r im et h yl-
silane) (21)22 with 5,15-diphenyl-10-(4-iodophenyl)-20-
(pyrid-4-yl)-21H,23H-porphine (14f) in the presence of
Pd dba and triphenylarsine (cf. ref 23) led to the por-
1
5-diphenylporphyrin 14f, on the other hand, required
more catalyst and a longer reaction time (24 h instead
of 3 h) than those of the 5,15-dialkylporphyrins 14a -e.
In a one-pot reaction, porphyrin 13 was deprotected
2
3
phyrin trimer 22a , the trimethylsilyl protecting groups
of which were removed to afford 22b. Coupling of the
latter with a large excess of 14f, using the same catalyst
as above, afforded the niphaphyrin hexadentate ligand
23 (Scheme 3).
with K
reacted in situ with triiodobenzene in the presence of
Pd(PPh (cf. ref 20), leading to the D -symmetric por-
2 3
CO and EtOH, and the liberated alkyne was
1
9
3
)
4
3
phyrin trimer 18 in 72% yield. Reaction of 14a -f with
triethynylbenzene8 in the presence of Pd(0) afforded the
corresponding trimers 19a -f. The yields of the reactions
were improved using triphenylarsine instead of tri-
phenylphosphine as the ligand for the palladium catalyst.
Whereas pentyl-, hexyl-, heptyl-, and phenylporphyrin
trimers 19c-f were obtained in fair yields (46-51%),
propyl and butyl trimers 19a ,b were obtained in only
Bin d in g P r op er ties of th e Ma cr ocycles. The for-
mation of supramolecular complexes between host mac-
rocycles 1 and guest trimers 18-20 (Figure 2) was first
investigated by UV/vis spectroscopy. Measurements at
,21
-
8
constant host concentration (∼10 M) were carried out
in CH Cl solutions at 20 °C. The obtained results show
2
2
the formation of a 1:1 complex between 1a ,d and 18,19a -
f, the stability constants of which were determined
experimentally from the titration curve by a nonlinear,
least-squares curve-fitting algorithm24 (Table 1). For all
(
18) Kruithof, K.; Schimtz, R. F.; Klumpp, G. Tetrahedron 1983, 39,
073-3081.
19) Ozasa, S.; Fujioka, Y.; Hashino, H.; Kimura, N.; Ibuki, E. Chem.
Pharm. Bull 1983, 31, 2313-2320.
20) Shultz, D. A.; Gwaltney, K. P.; Lee, H. J .Org. Chem. 1998, 63,
034-4038.
21) H u¨ bel, W.; Mer e´ nyi, R. Angew. Chem. 1962, 74, 781-782.
3
(
(22) Anthony, J . E.; Khan, S. I.; Rubin, Y. Tetrahedron Lett. 1997,
(
38, 3499-3502.
4
(23) Farina, V.; Krishnan, B. J . J . Am. Chem. Soc. 1991, 113, 9585-
(
9595.

Supramolecular Assemblies
J . Org. Chem., Vol. 66, No. 15, 2001 4977
Sch em e 3a
a
Reagents and conditions: (a) 1 (1 equiv), 2 (6 equiv), Pd2dba3, AsPh3, DMF/Et3N, 40 °C, 6 h (37%); (b) 1 M NaOH, THF (73%); (c) 3b
1 equiv), 2 (10 equiv), Pd2dba3, AsPh3, DMF/Et3N, 40 °C, 7 h (14%).
(
Ta ble 1. Bin d in g Con sta n ts (K) in CH2Cl2 a t 20 °C
betw een P or p h yr in Hexa m er s a n d Sta r -Sh a p ed
P or p h yr in Tr im er s
properties of the macrocycle. The main significance of the
long side chains is to improve the solubility of the
complex, which is of major importance for NMR mea-
surements (see below). Indeed, the concentrations re-
quired for NMR (∼10 M) are several orders of magni-
tude higher than those used for the determination of
stability constants by UV/vis spectroscopy. Ligand 19e
entry
host
guest
K (M-1)
-
4
9
1
2
3
4
5
6
7
8
9
1a
1a
1a
1a
1a
19a
19b
19c
19d
19e
19f
19e
18
2.6 × 10
2.0 × 10
4.3 × 10
3.8 × 10
2.2 × 10
5.3 × 10
1.1 × 10
1.4 × 10
7.1 × 10
3.5 × 10
9
9
9
9
9
1
9
8
9
binds to macrocycle Zn
strongly than to macrocycle Zn
3
Ni
3
(1d ) about 5 times more
(1a ) (Table 1, entries 7
6
1a
0
and 5). The fact that the binding constant of the same
ligand 19e with the linear hexamer 11f (entry 9) is still
high, although perceptibly lower than the stability con-
stants of the cyclic supramolecules, agrees with a tem-
plate effect of 19e on the conformation adopted by 11f.
Such kinds of supramolecular polyporphyrin assemblies
belong to the same type of complexes described by
1d
1d
11f
1d
19e
23
1
0
the entries of Table 1, high values of stability constants
are in good agreement with an effective three-center
chelation. (cf. refs 10b and 25).
27
28
Sanders et al. and, more recently, by Lindsey et al.
However, due to the high dilution used for the mea-
surements, no complexation could be observed with
macrocycle 1e as the host, because chelation of nitrogen-
containing ligands with Ni(II) is much less efficient than
as intermediates of template-directed syntheses of hex-
americ wheel porphyrins. In our hands, however, at-
tempts to synthesize macrocycles 1a -e in the presence
2
6
chelation with zinc. All the binding constants between
9
(27) (a) Vidal-Ferran, A.; M u¨ ller, C. M.; Sanders, J . K. M. J . Chem.
Soc., Chem. Commun. 1994, 2657-2658. (b) Anderson, S.; Anderson,
H. L.; Sanders, J . K. M. J . Chem. Soc., Perkin Trans. 1 1995, 2247-
macrocycle 1a and 19a -f are in the range 2 × 10 -5 ×
9
-1
1
0 M (Table 1, entries 1-6), so that the alkyl or aryl
2
254. (c) Anderson, S.; Anderson, H. L.; Sanders, J . K. M. J . Chem.
substituents seem to have little influence on the binding
Soc., Perkin Trans. 1 1995, 2255-2267.
(28) Li, J .; Ambrroise, A.; Yang, S. I.; Diers, J . R.; Seth, J .; Wack,
(
(
24) Conors, K. A. Binding Constants; Wiley: Chichester, 1987.
25) Anderson, H. L.; Sanders, J . K. M. J . Chem. Soc., Chem.
C. R.; Bocian, D. F.; Holten, D.; Lindsey, J . S. J . Am. Chem. Soc. 1999,
121, 8927-8940. Biemans, H. A. M.; Rowan, A. E.; Verhoeven, A.;
Vanoppen, P.; Latterini, L.; Foekema, J .; Schenning, A. P. H. J .; Meijer,
E. W.; de Schryver, F. C.; Nolte, R. J . M J . Am. Chem. Soc. 1998, 120,
11054-11060.
Commun. 1989, 1714-1715.
26) J ia, S.-L.; J entzen, W.; Shang, M.; Song, X.-Z.; Ma, J .-G.;
Scheidt, W. R.; Shelnutt, J . A. Inorg. Chem. 1998, 37, 4402-4412.
(

4
978 J . Org. Chem., Vol. 66, No. 15, 2001
Rucareanu et al.
F igu r e 2. Complexes 1d + 19e and 1d + 18 (mesityl groups at one of the meso positions on the zinc porphyrin rings of the
1
macrocyclic host have been omitted for clarity). Changes in H NMR chemical shifts on formation of the complexes are given (δ∆
in ppm).

Supramolecular Assemblies
J . Org. Chem., Vol. 66, No. 15, 2001 4979
thus confirming that 20 is too large to fit inside the cavity
of 1d .
Sp ect r oscop ic Ch a r a ct er iza t ion of t h e Su p r a -
m olecu la r Assem blies. As mentioned above, no com-
plexation could be observed with macrocycle 1e as the
1
host, either by UV/vis spectroscopy or by H NMR
spectroscopy. On the contrary, the complexation of mac-
3 3
rocycle Zn Ni (1d ) with both 18 and 19e could be
1
investigated by H NMR spectroscopy, which confirmed
the 1:1 stoichiometry of the supramolecular assemblies.
3
Measurements were performed at 298 K in CDCl , a
solvent in which the complexes exhibited a good solubil-
ity. A full assignment of the resonance signals was made
with the aid of COSY and NOE experiments, showing
that the three pyridine rings of the star-shaped ligand
bind to the three zinc ions of the macrocyclic host,
whereas the three nickel ions remain uncomplexed.
F igu r e 3. UV/vis binding curve for titration of 1d with 19e
in CH
2 2
Cl at 20 °C. The plot shows the measured points (9),
the calculated best fitting curve (s) for a binding constant of
1
0
-1
K ) 1.1 × 10
M , and the infinite binding limit (- - -).
The changes of the chemical shifts on formation of the
complexes are quoted in Figure 2. The protons on the
pyridine ring experience a large upfield shift (∆δ ) -6.06
ppm for the R-pyridine and -1.79 ppm for the â-pyridine
protons in complex 1d + 19e) due to the ring-current of
the porphyrin rings of the guest, which chelate Zn(II)
ions. In complex 1d + 19e, the upfield shift is observed
for all the protons of the guest, the intensity of this effect
decreasing with their distance to the zinc ion. In agree-
ment with the lower binding constant of complex 1d +
1
8, the upfield shifts of the protons on the pyridine of
the latter are smaller (∆δ ) -5.88 for the R-pyridine and
1.71 ppm for the â-pyridine protons) and decrease more
F igu r e 4. UV/vis binding curve for titration of 1d with 18 in
CH Cl at 20 °C. The plot shows the measured points (9), the
calculated best fitting curve (s) for a binding constant of K )
2
2
-
rapidly with distance than in complex 1d + 19e. Accord-
ing to the suggested structures of the supramolecular
assemblies, only insignificant changes are observed in the
chemical shifts of both the protons at the cornerstones
and at the Ni-chelated porphyrin rings of the host, which
are not involved in intermolecular bonding.
9
-1
1
.4 × 10 M , and the infinite binding limit (- - -).
Strong support for the suggested structures of the
above-described supramolecular complexes was obtained
by mass spectrometric measurements. The MALDI-TOF
spectrum (using dithranol as a matrix) of complex 1d +
1
9e revealed, in addition to the two peaks of the
individual guest and host (m/z ) 5623 and 2123, respec-
tively), a smaller peak at m/z ) 7747 for the supramo-
lecular complex, which confirms its 1:1 stoichiometry.
Similar results were obtained with the less strongly
bound complex 1d + 18 (m/z ) 7519) (m/z ) 5623 and
1896 for 1d and 18, respectively) and with the complex
between 1a and niphaphyrin 23 (m/z ) 9547.3). All
complexes were detected in positive mode as molecular
ions. Recently, it has been shown that MALDI-MS is a
suitable tool to study specific pseudorotaxane-like com-
plexes where ionic hydrogen bonds form the dominant
F igu r e 5. UV/vis binding curve for titration of 1e with 24 in
CH Cl at 20 °C. The plot shows the measured points (9), the
calculated best fitting curve (s) for a binding constant of K )
2
2
9
-1
3
.5 × 10 M , and the infinite binding limit (- - -).
of 19e as a template led to the formation of a larger
porphyrin oligomer (presumably a cyclic dodecamer)
instead of the desired macrocyclic hexamer. The inves-
tigation of this puzzling result is presently underway.
Finally, the influence of the diameter of the guest on
the stability of the supramolecular assemblies was
investigated by measuring the constants of association
between the macrocyclic hexamer 1d and three ligands
29
noncovalent interactions. These findings are extended
in the present work to complexes formed by multiple
electrostatic donor/acceptor interactions. The use of the
30
newly developed aprotic ET-matrix DCTB was espe-
cially promising. For the complex 1a + 23, the result was
an increase of almost 1 order of magnitude in signal
intensity of the peak at m/z ) 9547.3 compared to the
result obtained in the protic dithranol matrix
(18, 19e, and 20) of different sizes. As expected, the
highest value of the stability constant was observed with
trimer 19e. A value ca. 10 times lower was measured for
the smaller trimer 18, thus suggesting that some distor-
tion of the host molecule takes place in order to better
accommodate the guest (Figures 3-5). With the third
trimer 20, the stoichiometry of the complex is not 1:1,
(
29) Lehmann, E.; Salih, B.; G o´ mez-Lopez, M,; Diederich, F.; Zenobi,
R. Analyst 2000, 125, 849-854.
30) Ulmer, L.; Mattay, J .; Torres-Garcia H. G.; Luftmann, H. Eur.
J . Mass Spectrom. 2000, 6, 49-52
(

4
980 J . Org. Chem., Vol. 66, No. 15, 2001
Rucareanu et al.
Exp er im en ta l Section
(s, 54H), 1.84 and 1.85 (2 × s, 72H), 2.64 (s, 36H), 7.29 (s, 24H),
7
.75 (d, J ) 1.4, 12H), 7.86 (t, J ) 1.4, 6H), 7.97 and 8.25
Gen er a l Meth od s. All air- or water-sensitive reactions
(
8
4
AA′XX′, J AX ) 8.1, 8H), 7.97 and 8.27 (AA′XX′, J AX ) 8.1, 40H),
were carried out under argon. Solvents were generally dried
and distilled prior to use. Reactions were monitored by thin-
layer chromatography (TLC) on Merck silica gel 60 F254 (0.2
mm) precoated aluminum foil. Flash chromatography (FC):
Merck silica gel 60 (0.040-0.063 mm, 230-400 mesh), except
otherwise noted. Melting points (mp) were determined with a
hot stage apparatus (Thermovar, C. Reichert AG, Vienna)
equipped with a digital thermometer. UV/vis spectra were
recorded on a Hewlett-Packard 8452A diode-array or a Perkin-
Elmer Lambda 40 spectrometer; λmax (log ꢀ) in nm. NMR:
.73 and 8.83 (2 × d, J ) 4.4, 8H), 8.81 and 8.93 (2 × d, J )
.8, 40H); UV/vis (CH Cl ) 292, 424, 515, 550, 590, 647; UV/
2
2
vis (benzene) 289, 427, 516, 551, 592, 648; MALDI-MS (dithra-
+
nol) m/z 5580.7 ([M + H] ) (calcd average mass for C384
Zn 5579.67).
Ma cr ocyclic p or p h yr in h exa m er 1d was obtained from
1h (5.0 mg, 0.869 µmol), as described for 1a . In different
batches the yield oscillated between 0.73 and 1.51 mg (15-
302 24
H N -
5
1
1%): 1H NMR (500.13 MHz, CDCl
) δ 1.48 (s, 54H), 1.82 (s,
6H), 1.84 (s, 36H), 2.58 (s, 18H), 2.63 (s, 18H), 7.22 (s, 12H),
.29 (s, 12H), 7.72 (t, J ) 1.5, 6H), 7.74 (t, J ) 1.5, 6H), 7.82
t, J ) 1.4, 6H), 7.90 and 8.07 (AA′XX′, J AX ) 8.2, 24H), 7.96
3
3
7
3
1
13
Varian Gemini 200 ( H, 200.00 MHz; C: 50.30 MHz), Bruker
1
1
AM 360 ( H, 360.14 MHz), or Bruker Avance DRX 500 ( H:
(
1
3
5
00.13 MHz, C: 125.76 MHz), in CDCl
3
solutions unless
otherwise stated; H and 13C chemical shifts (δ) are given in
ppm relative to Me Si as internal standard, J values in Hz.
and 8.26 (AA′XX′, J AX ) 8.2, 24H), 8.63 and 8.74 (2 × d, J )
.8, 24H), 8.81 and 8.91 (2 × d, J ) 4.8, 24H); UV/vis (CH
Cl ) 290, 423, 533, 548, 590; MALDI-MS (dithranol) m/z 5623.3
300 3 3
[M + H] ) (calcd average mass for C384H N24Ni Zn 5622.99);
1
4
2
-
4
2
Mass spectra: Vacuum Generators Micromass 7070E instru-
ment equipped with a data system DS 11-250, EI (electron
ionization): acceleration voltage 70 eV, FAB (fast atom
bombardment): in 3-nitrobenzyl alcohol with Ar at 8 kV; ES -
MS (electrospray ionization, positive mode) and MALDI-MS-
+
(
+
4+
ES -MS (THF/HCOOH) m/z 1359.1 [M - 3Zn + 10H] , 1087.5
[
5+
M - 3Zn + 11H]
Ma cr ocyclic P or p h yr in Hexa m er 1e. To a solution of 1d
1.14 mg, 0.203 µmol) in CHCl (2 mL) was added TFA (200
.
+
(
3
(
Matrix Assisted Laser Desorption Ionization): FT mass
µL), and the mixture was stirred at 20 °C for 2 h. The mixture
was diluted with CHCl (10 mL), and then saturated aqueous
NaHCO was added. The organic layer was separated, washed
with water, and dried (MgSO ) before the solvent was evapo-
rated. The residue was purified by FC (CHCl /hexane 60:40)
to yield 0.84 mg (76%) of 1e: 1H NMR (360.14 MHz, CDCl
) δ
2.61 (s, 6H), 1.48 (s, 54H), 1.82 (s, 36H), 1.85 (s, 36H), 2.58
s, 18H), 2.63 (s, 18H), 7.22 (s, 12H), 7.29 (s, 12H), 7.73 (2 ×
t, J ) 1.5, 12H), 7.82 (t, J ) 1.5, 6H), 7.90 and 8.07 (AA′XX′,
AX ) 8.2, 24H), 7.96 and 8.24 (AA′XX′, J AX ) 8.2, 24H), 8.63
and 8.74 (2 × d, J ) 4.8, 24H), 8.72 and 8.83 (2 × d, J ) 4.8,
4H); UV/vis (CH Cl ) 289, 421, 521, 550, 591, 647; MALDI-
MS (dithranol) m/z 5433.3 ([M + H] ) (calcd average mass for
5432.90).
5,15-Bis(4-iod op h en yl)-10,20-bis(m esityl)p or p h in a to-
2-)]n ick el (2c). To a solution of 5,15-bis(4-iodophenyl)-10,-
spectrometer Bruker 4.7T BioAPEX II; MALDI-TOF: Bruker
Reflex-II (delayed extraction, 20 kV acc. voltage, positive
reflection mode) using dithranol (1,8,9-anthracenetriol) or
DCTB (2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enyliden-
3
3
4
3
3
1
e]malonitrile) dissolved in CHCl
droplet method) and averaging 200-1100 shots. Tetrakis-
triphenylphosphine)palladium, tris(dibenzylideneacetone)di-
palladium (Pd dba ), triphenylarsine, and tetrabutylammoni-
um fluoride (TBAF) were purchased from Aldrich Chemie (CH-
471 Buchs); dimethylformamide (DMF), trifluoroacetic acid
TFA), tetrahydrofuran (THF), trimethylsilylacetylene (TMSA),
and other reagents from Fluka Chemie AG (CH-9471 Buchs).
3
(0.05 M) as matrix (dried
3
-
(
(
2
3
J
9
(
2
2
2
+
1
3
9
Porphyrins 2a and 2b were prepared according to described
procedures.
C
384 306 3
H N24Ni
[
Ma cr ocyclic P or p h yr in Hexa m er 1a . Air was removed
from a solution of 11b (6.2 mg, 1.07 µmol) in 4.28 mL of DMF/
(
2
11
0-bis(mesityl)porphine (2a ) (620 mg, 0.652 mmol) in 62 mL
/AcOH (9:1) was added nickel acetate tetrahydrate
2.92 g, 11.7 mmol), and the mixture was refluxed for 48 h.
Thereafter, CHCl (200 mL) and water (200 mL) were added.
The organic layer was separated, washed with water, and dried
MgSO ). The residue obtained after removal of the solvent
was purified by FC (CHCl /hexane 35:65) to yield 624 mg (95%)
of 2c: H NMR (360.14 MHz) δ 1.79 (s, 12H), 2.58 (s, 6H),
.21 (s, 4H), 7.77 and 8.01 (AA′XX′, J AX ) 8.1, 8H), 8.60 (d, J
4.8, 4H), 8.67 (d, J ) 4.8, 4H); UV/vis (CH Cl ) 295 (3.78),
14 (5.36), 528 (4.19); ES -MS (THF/MeOH) m/z 1007.64 (M )
Anal. Calcd for C50 Ni (1007.39): C, 59.61; H, 3.80; N,
.56. Found: C, 59.40; H, 3.96; N, 5.64.
-[3-(1,1-Dim eth yleth yl)-5-eth yn ylp h en yl]-3,3-d ieth yl-
-tr ia zen e (3). To a solution of 1-[3-(1,1-dimethylethyl)-5-
Et
6.2 mg, 5.36 µmol) was added, deaeration was continued for
0 min, and then the mixture was heated at 40 °C for 6 h.
The solvent was subsequently removed under reduced pres-
sure, and the crude product was purified by 2-fold FC (CHCl
3 3 4
N (5:1) by passing argon through it for 30 min. Pd(PPh )
of CHCl
3
(
1
(
3
3
/
(
4
hexane, gradient from 60:40 to 80:20) and finally by MPLC
3
using a Lobar column (Lichroprep Si60, 40-63 µm, Merck),
1
1
provided 1.80 mg (30%) of 1a : H NMR (500.13 MHz, CDCl
3
)
7
δ 1.49 (s, 54H), 1.84 (s, 72H), 2.64 (s, 36H), 7.29 (s, 24H), 7.75
d, J ) 1.4, 12H), 7.86 (t, J ) 1.4, 6H), 7.97 and 8.27 (AA′XX′,
AX ) 8.3, 48H), 8.81 and 8.92 (2 × d, J ) 4.6, 48H); UV/vis
CH Cl ) 292, 425, 550, 590; UV/vis (benzene) 289, 427, 551,
92; MALDI-MS (dithranol) m/z 5644.1 ([M + H] ) (calcd
)
4
2
2
(
J
+
+
38 2 4
H I N
(
5
2
2
5
+
1
+
average mass for C384
300 6 3
H N24Zn 5643.03); ES -MS (CHCl /
1
3
+
MeOH/HCOOH) m/z 1755.2 ([M - 6Zn + 15H] ), 1316.6 ([M
-
6
12
[(trimethylsilyl)ethynyl]phenyl]-3,3-diethyl-1-triazene (111.6
4
+
5+
6Zn + 16H] ), 1053.5 ([M - 6Zn + 17H] ), 878.1 ([M -
6
mg, 0.339 mmol) in 11 mL of THF was added TBAF (1M in
THF, 0.35 mL, 0.35 mmol), and the mixture was stirred for
+
Zn + 18H] ).
Ma cr ocyclic P or p h yr in Hexa m er 1b. Reaction of 11d
10 min at 20 °C. A few grains of CaCl were added to remove
2
(
6.3 mg, 1.13 µmol), as described for 1a , afforded 0.95 mg (15%)
any excess of fluoride, and the solvent was evaporated. The
crude product was purified by FC (CH Cl /hexane 1:4) to yield
1
of 1b: H NMR (500.13 MHz, CDCl
5
7
3
) δ -2.61 (s, 6H), 1.49 (s,
4H), 1.84 and 1.85 (2 × s, 72H), 2.63 (s, 36H), 7.29 (s, 24H),
.75 (d, J ) 1.4, 12H), 7.86 (t, J ) 1.4, 6H), 7.97 and 8.25
2
2
1
75.9 mg (87%) of 3 as a white solid: mp 45-46 °C; H NMR
(360.14 MHz, CDCl ) δ 1.27 (br s, 6H), 1.33 (s, 9H), 3.02 (s,
3
(
AA′XX′, J AX ) 8.1, 24H), 7.97 and 8.27 (AA′XX′, J AX ) 8.1,
4H), 8.73 and 8.84 (2 × d, J ) 4.4, 24H), 8.81 and 8.92 (2 ×
d, J ) 4.8, 24H); UV/vis (CH Cl ) 292, 423, 516, 550, 592, 648;
UV/vis (benzene) 289, 425, 516, 551, 593, 650; MALDI-MS
1H), 3.76 (q, J ) 7.0, 4H), 7.29 (t, J ) 1.8, 1H), 7.39 (t, J )
2
1.8, 1H), 7.42 (t, J ) 1.8, 1H); 13C NMR (50 MHz, CDCl ) δ
3
2
2
12.7, 12.8, 31.2, 34.7, 44.0, 75.8, 84.6, 119.5, 120.45, 121.8,
+
125.9, 151.0, 151.9; EI-MS m/z 257 (M
). Anal. Calcd for
+
(
C
2
dithranol) m/z 5453.9 ([M + H] ) (calcd average mass for
C H23N3 (257.38): C, 74.67; H, 9.01; N, 16.33. Found: C,
1
6
+
384
H
306
N
24Zn
3
5452.94); ES -MS (THF) m/z 2727.4 [M +
74.97; H, 9.28; N, 16.01.
5-[4-[[3-(3,3-Dieth yl-1-tr ia zen yl)-5-(1,1-d im eth yleth yl)-
H]2 , 1818.6 [M + 3H]
Ma cr ocyclic P or p h yr in Hexa m er 1c. Reaction of 11f (5.0
mg, 0.876 µmol), as described for 1a , afforded 0.39 mg (8%) of
+
3+
.
[
ph en yl]eth yn yl]ph en yl]-15-(4-iodoph en yl)-10,20-bis(2,4,6-
tr im eth ylp h en yl)p or p h in a to(2-)]zin c (4a ). Air was re-
1
8
pure 1c: H NMR (500.13 MHz, CDCl
3
) δ -2.61 (s, 2H), 1.49
moved from a solution of 2b (1.70 g, 1.68 mmol) and 3 (0.432
g, 1.68 mmol) in 378 mL of DMF/Et
for 30 min. Then, Pd(PPh (193.7 mg, 0.168 mmol) was added,
and deaeration was continued for 10 min. Thereafter, the
3
N (5:1) by blowing argon
(
31) Yellow crystals of DCTB (mp 124 °C) were a gift from H.
3 4
)
Luftmann (cf. ref 30).

Supramolecular Assemblies
J . Org. Chem., Vol. 66, No. 15, 2001 4981
mixture was heated at 40 °C for 14 h. The solvent was removed
under reduced pressure, and the crude product was purified
by FC. Three fractions were obtained: unreacted 2b (0.370 g;
[5-[4-[[3-(1,1-Dim et h ylet h yl)-5-iod op h en yl]et h yn yl]-
ph en yl]-10,20-bis(2,4,6-tr im eth ylph en yl)-15-[4-[(tr im eth yl-
silyl)eth yn yl]p h en yl]-21H,23H-p or p h in a to(2-)]zin c (5a ).
To a thick-walled screw cap tube was added a solution of 4b
(210 mg, 0.188 mmol) in iodomethane (21 mL). The tube was
flushed with argon and then screwed and heated to 135 °C
for 2 h. The reaction mixture was cooled to room temperature,
and the solvent was removed under reduced pressure. The
2
2%), 4a (0.796 g; 41%), and 5,15-bis[4-[[3-(3,3-diethyl-1-
triazenyl)-5-(1,1-dimethylethyl)phenyl]ethynyl]phenyl]-10,20-
bis(mesityl)porphinato(2-)]zinc (0.640 g; 30%), which were
successively eluted using CHCl
3
/hexane/Et
3
N (gradient from
1
5
1
3
0:50:0.2 to 65:35:0.2). 4a : H NMR (360.14 MHz, CDCl ) δ
.32 (t, J ) 7.3, 6H), 1.42 (s, 9H), 1.82 (s, 12H), 2.63 (s, 6H),
.82 (q, J ) 7.3, 4H), 7.29 (s, 4H), 7.49 (d, J ) 1.8, 2H), 7.58
3
crude product was purified by FC (CHCl
3 3
/hexane/Et N 50:50:
0.1) to yield 211 mg (98%) of 5a : 1H NMR (360.14 MHz, CDCl
)
3
(
t, J ) 1.8, 1H), 7.93 and 8.07 (AA′XX′, J AX ) 8.2, 4H), 7.97
δ 0.38 (s, 9H), 1.38 (s, 9H), 1.83 (s, 12H), 2.63 (s, 6H), 7.28 (s,
4H), 7.65 (t, J ) 1.5, 1H), 7.74 (t, J ) 1.5, 1H), 7.85 (t, J )
1.5, 1H), 7.86 and 8.18 (AA′XX′, J AX ) 7.9, 4H), 7.91 and 8.23
(AA′XX′, J AX ) 7.9, 4H), 8.78 and 8.85 (2 × d, J ) 4.6, 4H),
and 8.22 (AA′XX′, J AX ) 8.6, 4H), 8.79 and 8.86 (2 × d, J )
4
2
.9, 4H), 8.79 and 8.90 (2 × d, J ) 4.9, 4H); UV/vis (CH
96 (4.71), 422 (5.75), 550 (4.38), 584 (3.67), 592 (3.66); FAB-
Zn (1143.53): C,
9.32; H, 5.29; N, 8.57. Found: C, 69.54; H, 5.48; N, 8.44.
5-[4-[[3-(3,3-Dieth yl-1-tr ia zen yl)-5-(1,1-d im eth yleth yl)-
2 2
Cl )
MS m/z 1143.1. Anal. Calcd for C66
H
60IN
7
8.78 and 8.89 (2 × d, J ) 4.6, 4H); UV/vis (CH
2 2
Cl ) 292 (4.34),
422 (5.52), 550 (4.17), 590 (3.52); FAB-MS m/z 1141.1. Anal.
Calcd for C67 SiZn (1140.60): C, 70.55; H, 5.21; N, 4.91.
6
[
H59IN
4
p h en yl]et h yn yl]p h en yl]-10,20-b is(2,4,6-t r im et h ylp h en -
yl)-15-[4-[(t r im et h ylsilyl)et h yn yl]p h en yl]p or p h in a t o-
Found: C, 70.96; H, 5.12; N, 5.06.
5-[4-[[3-(1,1-Dim e t h yle t h yl)-5-iod op h e n yl]e t h yn yl]-
p h en yl]-10,20-bis(2,4,6-tr im eth ylp h en yl)-15-[4-[(tr im eth -
ylsilyl)eth yn yl]p h en yl]-21H,23H-p or p h in e (5b). To a solu-
(
2-)]zin c (4b). Air was removed from a solution of 4a (0.796
g, 0.696 mmol) in 144 mL of DMF/Et N (5:1) by blowing argon
for 20 min. Then, Pd(PPh Cl (48.9 mg, 69.6 µmol), CuI (26.5
3
3
)
2
2
tion of 5a (212 mg, 0.186 mmol) in CHCl
TFA (6.6 mL), and the mixture was stirred at 20 °C for 2 h.
The mixture was diluted with CHCl (80 mL), and then
saturated aqueous NaHCO was added. The organic layer was
separated, washed with water, and dried (MgSO ) before the
solvent was evaporated. The residue was purified by FC
3
(66 mL) was added
mg, 139.2 µmol), and trimethylsilylacetylene (289 µL, 2.09
mmol) were added. Thereafter, the mixture was heated at 35
3
°
C for 14 h. The solvent was removed under reduced pressure,
and the crude product was purified by FC (CHCl /hexane/Et
0:50:0.2 then 65:35:0.2) to yield 0.708 g (91%) of 4b: 1H NMR
360.14 MHz, CDCl
3
3
3
N
4
5
1
(
(
(
8
7
3
) δ 0.37 (s, 9H), 1.32 (t, J ) 7.3, 6H), 1.42
(CHCl
(360.14 MHz, CDCl
3
/hexane 50:50) to yield 137 mg (68%) of 5b: H NMR
) δ -2.64 (s, 2H), 0.37 (s, 9H), 1.38 (s, 9H),
s, 9H), 1.82 (s, 12H), 2.63 (s, 6H), 3.83 (q, J ) 7.3, 4H), 7.28
s, 4H), 7.49 (d, J ) 1.6, 2H), 7.58 (t, J ) 1.6, 1H), 7.85 and
3
1.83 (s, 12H), 2.63 (s, 6H), 7.28 (s, 4H), 7.65 (t, J ) 1.7, 1H),
7.74 (t, J ) 1.7, 1H), 7.85 (t, J ) 1.7, 1H), 7.86 and 8.16
(AA′XX′, J AX ) 8.4, 4H), 7.91 and 8.21 (AA′XX′, J AX ) 8.4, 4H),
8.70 and 8.75 (2 × d, J ) 4.8, 4H), 8.71 and 8.80 (2 × d, J )
.18 (AA′XX′, J AX ) 7.6, 4H), 7.93 and 8.22 (AA′XX′, J AX )
.6, 4H), 8.78 and 8.85 (2 × d, J ) 4.7, 4H), 8.78 and 8.90 (2
d, J ) 4.7, 4H); UV/vis (CH Cl ) 298 (4.57), 422 (5.64), 550
4.29), 584 (3.72); FAB-MS m/z 1114.5. Anal. Calcd for
SiZn (1113.84): C, 76.56; H, 6.24; N, 8.80. Found: C,
5.97; H, 6.39; N, 8.96.
5-[4-[[3-(3,3-Dieth yl-1-tr ia zen yl)-5-(1,1-d im eth yleth yl)-
×
2
2
(
2 2
4.8, 4H); UV/vis (CH Cl ) 288 (4.54), 420 (5.64), 516 (4.29), 550
+
C
7
71
H
69
N
7
(4.03), 590 (3.86), 646 (3.72); ES -MS (CHCl
3
/MeOH) m/z
+
1078.1 ([M + H] ).
[
[5-[4-[[3-(1,1-Dim et h ylet h yl)-5-iod op h en yl]et h yn yl]-
p h en yl]-10,20-bis(2,4,6-tr im eth ylp h en yl)-15-[4-[(tr im eth -
ylsilyl)eth yn yl]p h en yl]-21H,23H-p or p h in a to(2-)]n ick el
ph en yl]eth yn yl]ph en yl]-15-(4-iodoph en yl)-10,20-bis(2,4,6-
tr im eth ylp h en yl)p or p h in a to(2-)]n ick el (4c). Reaction of
2
c (575 mg, 0.571 mmol) with 3 (146.9 mg, 0.571 mmol) in
(5c). Reaction of 4d (205 mg, 0.185 mmol) in CH
as described for 5a , with subsequent purification by FC
(CHCl /hexane/Et N 40:60:0.1), afforded 206 mg (98%) of 5c:
H NMR (360.14 MHz, CDCl ) δ 0.35 (s, 9H), 1.36 (s, 9H), 1.80
3
I (20.5 mL),
the presence of Pd(PPh
DMF/Et N, as described for 4a , with subsequent purification
by FC, afforded three fractions: unreacted 2c (278 mg; 48%),
3 4
) (65.9 mg, 57.1 µmol) in 132 mL of
3
3
3
1
3
4
c (196 mg; 30%), and 5,15-bis-[4-[[3-(3,3-diethyl-1-triazenyl)-
(s, 12H), 2.57 (s, 6H), 7.21 (s, 4H), 7.62 (t, J ) 1.5, 1H), 7.73
(t, J ) 1.5, 1H), 7.78 and 7.98 (AA′XX′, J AX ) 8.5, 4H), 7.83 (t,
J ) 1.5, 1H), 7.84 and 8.04 (AA′XX′, J AX ) 8.5, 4H), 8.60 and
5
-(1,1-dimethylethyl)phenyl]ethynyl]phenyl]-10,20-bis(mesityl)-
porphinato(2-)]nickel (110 mg; 15%), which were successively
eluted using CHCl /hexane/Et N (gradient from 35:65:0.2 to
0:50:0.2). 4c: H NMR (360.14 MHz, CDCl ) δ 1.31 (t, J )
3
3
8.66 (2 × d, J ) 4.9, 4H), 8.60 and 8.70 (2 × d, J ) 4.9, 4H);
1
+
5
7
7
1
4
3
UV/vis (CH
2
Cl
2
) 289 (4.55), 416 (5.37), 528 (4.26); ES -MS
+
.3, 6H), 1.40 (s, 9H), 1.80 (s, 12H), 2.57 (s, 6H), 3.81 (q, J )
.3, 4H), 7.21 (s, 4H), 7.46 (t, J ) 1.7, 1H), 7.48 (t, J ) 1.7,
H), 7.55 (t, J ) 1.7, 1H), 7.78 and 8.01 (AA′XX′, J AX ) 8.2,
H), 7.85 and 8.02 (AA′XX′, J AX ) 8.2, 4H), 8.60 and 8.67 (2 ×
4
(THF/HCOOH) m/z 1133.9 (M ). Anal. Calcd for C67H59IN -
NiSi (1133.92): C, 70.97; H, 5.24; N, 4.94. Found: C, 71.24;
H, 4.97; N, 4.87.
[5-[4-[[3-(3,3-Dieth yl-1-tr ia zen yl)-5-(1,1-d im eth yleth yl)-
p h en yl]eth yn yl]p h e n yl]-15-(4-eth yn ylp h en yl)-10,20-bis-
(2,4,6-tr im eth ylph en yl)-21H,23H-por ph in ato(2-)]zin c (6).
To a solution of 4b (270 mg, 0.242 mmol) in THF (40 mL) was
added aqueous NaOH (1 M, 22.5 mL), and the mixture was
stirred vigorously at 20 °C for 3 h. After evaporation of the
d, J ) 4.8, 4H), 8.60 and 8.71 (2 × d, J ) 4.8, 4H); UV/vis
+
(CH
2
Cl
2
) 292 (4.66), 415 (5.38), 527 (4.25); ES -MS (THF/
+
+
HCOOH) m/z 1137.62 ([M + H] ), 1037.6 ([M - N
Anal. Calcd for C66 Ni (1136.85).: C, 69.73; H, 5.32; N,
.62. Found: C, 69.56; H, 5.55; N, 8.72.
5-[4-[[3-(3,3-Dieth yl-1-tr ia zen yl)-5-(1,1-d im eth yleth yl)-
ph en yl]eth yn yl]ph en yl]-10,20-bis(2,4,6-tr im eth ylph en yl)-
5-[4-[(t r im et h ylsilyl)et h yn yl]p h en yl]p or p h in a t o(2-)]-
n ick el (4d ). Reaction of 4c (234 mg, 0.206 mmol) with TMSA
86.6 µL, 0.625 mmol) in the presence of Pd(PPh (14.6 mg,
0.9 µmol) and CuI (7.9 mg, 41.7 µmol) in 42 mL of DMF/Et N,
as described for 4b, with subsequent purification by FC
3 2
Et + H] ).
H
60IN
7
8
[
THF, CH
organic layer was separated, washed with water, and dried
(MgSO ). The residue obtained after removal of the solvent
was purified by FC (CHCl /hexane/Et N 55:45:0.2) to yield 248
mg (98%) of 6: H NMR (360.14 MHz, CDCl ) δ 1.32 (t, J )
2 2
Cl (60 mL) and water (60 mL) were added. The
1
4
3
3
1
(
2
3
)
4
3
3
7.0, 6H), 1.42 (s, 9H), 1.82 (s, 12H), 2.63 (s, 6H), 3.30 (s, 1H),
3.83 (q, J ) 7.0, 4H), 7.28 (s, 4H), 7.49 (d J ) 1.5, 2H), 7.58 (t,
J ) 1.5, 1H), 7.87 and 8.20 (AA′XX′, J AX ) 7.6, 4H), 7.93 and
8.22 (AA′XX′, J AX ) 7.9, 4H), 8.78 and 8.85 (2 × d, J ) 4.6,
(
(
(
(
1
8
CHCl
3
/hexane/Et
3
N 50:50:0.2 then 65:35:0.2), afforded 205 mg
) δ 0.35 (s, 9H), 1.31
1
90%) of 4d : H NMR (360.14 MHz, CDCl
3
t, J ) 7.3, 6H), 1.40 (s, 9H), 1.80 (s, 12H), 2.57 (s, 6H), 3.81
q, J ) 7.3, 4H), 7.21 (s, 4H), 7.46 (t, J ) 1.7, 1H), 7.48 (t, J )
4H), 8.78 and 8.90 (2 × d, J ) 4.6, 4H); UV/vis (CH
2 2
Cl ) 296
(4.66), 422 (5.70), 550 (4.33), 590 (3.67); FAB-MS m/z 1042.9.
Anal. Calcd for C68 Zn (1041.66): C, 78.40; H, 5.90; N,
.7, 1H), 7.55 (t, J ) 1.7, 1H), 7.78 and 7.98 (AA′XX′, J AX
)
61 7
H N
.5, 4H), 7.85 and 8.02 (AA′XX′, J AX ) 8.5, 4H), 8.60 and 8.66
9.41. Found: C, 78.22; H, 6.12; N, 9.36.
(
(
2 × d, J ) 4.9, 4H), 8.60 and 8.71 (2 × d, J ) 4.9, 4H); UV/vis
[µ-[5-[4-[[3-[[4-[10,20-Bis(2,4,6-tr im eth ylp h en yl)-15-[4-
+
CH
2
Cl
2
) 292 (4.68), 416 (5.38), 528 (4.27); ES -MS (THF/
[(tr im eth ylsilyl)eth yn yl]p h en yl]-21H,23H-p or p h in -5-yl-
+
+
21
22
23
24
HCOOH) m/z 1108.0 ([M + H] ), 1007.9 ([M - N
Anal. Calcd for C71 NiSi (1107.16): C, 77.02; H, 6.28; N,
.86. Found: C, 76.95; H, 6.03; N, 8.93.
3
Et
2
+ H] ).
N ,N ,N ,N ]p h en yl]et h yn yl]-5-(1,1-d im et h ylet h yl)-
H
69
N
7
ph en yl]eth yn yl]ph en yl]-15-[4-[[3-(3,3-dieth yl-1-tr iazen yl)-
5-(1,1-d im et h ylet h yl)p h en yl]et h yn yl]p h en yl]-10,20-b is-
8

4
982 J . Org. Chem., Vol. 66, No. 15, 2001
Rucareanu et al.
(
N
2,4,6-t r im e t h ylp h e n yl)-21H ,23H -p or p h in a t o
,N ,N ,N ]]d izin c (7a ). Air was removed from a solution
(4-)-
5a , with subsequent purification by FC (CHCl
55:45:0.1), afforded 180 mg (94%) of 8a : 1H NMR (360.14 MHz,
CDCl ) δ 0.38 (s, 9H), 1.38 (s, 9H), 1.49 (s, 9H), 1.83 (s, 12H),
3 3
/hexane/Et N
2
1
22
23
24
of 5a (0.357 g, 0.313 mmol) and 6 (0.335 g, 0.322 mmol) in
44 mL of DMF/Et N (5:1) by passing argon through it for 30
min. Pd(PPh (54.3 mg, 0.047 mmol) was added, deaeration
3
1
3
1.84 (s, 12H), 2.64 (s, 12H), 7.29 (s, 8H), 7.66 (t J ) 1.5, 1H),
7.74 (t, J ) 1.5, 1H), 7.75 (d, J ) 1.5, 2H), 7.84 (t, J ) 1.5,
1H), 7.86 (t, J ) 1.5, 1H), 7.86 and 8.18 (AA′XX′, J AX ) 8.4,
4H), 7.92 and 8.24 (AA′XX′, J AX ) 8.2, 4H), 7.98 and 8.26
(AA′XX′, J AX ) 8.1, 8H), 8.78 and 8.85 (2 × d, J ) 4.7, 4H),
8.80 and 8.89 (2 × d, J ) 4.7, 4H), 8.81 and 8.92 (2 × d, J )
4.6, 4H), 8.81 and 8.93 (2 × d, J ) 4.6, 4H); UV/vis (CH Cl )
3 4
)
was continued for 10 min, and then the mixture was heated
at 40 °C for 14 h. The solvent was subsequently removed under
reduced pressure, and the crude product was purified by FC
(
CHCl
3
/hexane/Et
H NMR (360.14 MHz, CDCl
H), 1.42 (s, 9H), 1.49 (s, 9H), 1.84 (s, 24H), 2.64 (s, 12H), 3.82
q, J ) 7.1, 4H), 7.29 (s, 8H), 7.49 (d J ) 1.5, 2H), 7.59 (t, J )
3
N 60:40:0.2) to yield 0.588 g (91%) of 7a :
1
3
) δ 0.38 (s, 9H), 1.32 (t, J ) 7.1,
2
2
+
6
(
1
8
8
290 (4.90), 422 (5.93), 550 (4.64), 590 (4.03); ES -MS (CHCl /
3
MeOH) m/z 1040.3 (M2 ) (calcd average mass for C131H109IN8-
SiZn2 2081.11).
+
.5, 1H), 7.75 (d, J ) 1.5, 2H), 7.84 (t, J ) 1.5, 1H), 7.86 and
.19 (AA′XX′, J AX ) 8.4, 4H), 7.93 and 8.23 (AA′XX′, J AX
.2, 4H), 7.98 and 8.26 (AA′XX′, J AX ) 8.2, 4H), 7.98 and 8.27
)
[
5-[4-[[3-[[4-[10,20-Bis(2,4,6-tr im eth ylph en yl)-15-[4-[(tr i-
m e t h ylsilyl)e t h yn yl]p h e n yl]-21H ,23H -p or p h in -5-yl]-
p h en yl]et h yn yl]-5-(1,1-d im et h ylet h yl)p h en yl]et h yn yl]-
phenyl]-15-[4-[[3-(1,1-dimethylethyl)-5-iodophenyl]ethynyl]-
p h en yl]-10,20-b is(2,4,6-t r im et h ylp h en yl)-21H ,23H -p or -
(
AA′XX′, J AX ) 8.2, 4H), 8.79 and 8.85 (2 × d, J ) 4.6, 4H),
8
2
4
.80 and 8.91 (2 × d, J ) 4.6, 4H), 8.81 (2 × d, J ) 4.6, 2 ×
H), 8.92 (2 × d, J ) 4.6, 2 × 2H); UV/vis (CH Cl ) 294 (5.00),
22 (5.93), 512 (4.06), 550 (4.67), 590 (4.13); ES -MS (CHCl
2
2
+
3
/
21
22
23
24
p h in a to(2-)-N ,N ,N ,N ]zin c (8b). Reaction of 7b (114.5
2
+
MeOH) m/z 1027.2 (M ) (calcd average mass for C135
SiZn 2054.34).
5-[4-[[3-[[4-[10,20-Bis(2,4,6-tr im eth ylph en yl)-15-[4-[(tr i-
m e t h ylsilyl)e t h yn yl]p h e n yl]-21H ,23H -p or p h in -5-yl]-
p h en yl]eth yn yl]- 5-(1,1-d im eth yleth yl)p h en yl]eth yn yl]-
ph en yl]-15-[4-[[3-(3,3-dieth yl-1-tr ia zen yl)-5-(1,1-dim eth yl-
eth yl)p h en yl]eth yn yl]p h en yl]-10,20-bis(2,4,6-tr im eth yl-
119 11
H N -
mg, 57.5 µmol), as described for 5a , with subsequent purifica-
2
tion by 2-fold FC (CHCl
3
/hexane/Et
mg (51%) of 8b: H NMR (360.14 MHz, CDCl
H), 0.37 (s, 9H), 1.38 (s, 9H), 1.49 (s, 9H), 1.84 (s, 24H), 2.64
3
N 50:50:0.1), afforded 58.9
[
1
3
) δ -2.63 (s,
2
(
s, 12H), 7.29 (s, 8H), 7.66 (t J ) 1.4, 1H), 7.75 (m, 3H), 7.84
(t, J ) 1.4, 1H), 7.86 (t, J ) 1.4, 1H), 7.86 and 8.17 (AA′XX′,
J
AX ) 8.1, 4H), 7.92 and 8.24 (AA′XX′, J AX ) 8.1, 4H), 7.98
2
1
22
23
24
ph en yl)-21H,23H-por ph in ato(2-)-N ,N ,N ,N ]zin c (7b).
Reaction of 5b (0.306 g, 0.284 mmol) with 6 (0.304 g, 0.292
and 8.25 (AA′XX′, J AX ) 8.1, 4H), 7.98 and 8.27 (AA′XX′, J AX
8.1, 4H), 8.71 and 8.76 (2 × d, J ) 4.8, 4H), 8.73 and 8.84
2 × d, J ) 4.8, 4H), 8.81 and 8.90 (2 × d, J ) 4.6, 4H), 8.82
Cl ) 288 (4.95), 422
5.84), 516 (4.37), 548 (4.49), 588 (4.23), 644 (3.99); ES -MS
)
(
mmol) in the presence of Pd(PPh
0 mL of DMF/Et N, as described for 7a , with subsequent
purification by FC (CHCl /hexane/Et N 60:40:0.2), afforded
.370 g (92%) of 7b: H NMR (360.14 MHz, CDCl ) δ -2.63
3 4
) (31.5 mg, 0.027 mmol) in
9
3
and 8.93 (2 × d, J ) 4.6, 4H); UV/vis (CH
2
2
3
3
+
(
(
1
0
(
9
8
1
8
3
+
2+
CHCl
78.2 ([M - Zn + 4H] ) (calcd average mass for C131
SiZn 2017.74).
3
/MeOH) m/z 2018.6 ([M + H] ), 1009.4 ([M + 2H] ),
s, 2H), 0.37 (s, 9H), 1.32 (t, J ) 7.3, 6H), 1.42 (s, 9H), 1.49 (s,
2+
9
8
H111IN -
H), 1.84 (s, 24H), 2.64 (s, 12H), 3.80 (q, J ) 7.3, 4H), 7.29 (s,
H), 7.49 (d J ) 1.8, 2H), 7.58 (t, J ) 1.8, 1H), 7.75 (dd, J )
[
µ-[5-[4-[[3-[[4-[10,20-Bis(2,4,6-tr im eth ylp h en yl)-15-[4-
.5, 2H), 7.84 (t, J ) 1.5, 1H), 7.86 and 8.16 (AA′XX′, J AX
)
[
N
(tr im eth ylsilyl)eth yn yl]p h en yl]-21H,23H-p or p h in -5-yl-
.5, 4H), 7.93 and 8.22 (AA′XX′, J AX ) 8.5, 4H), 7.97 and 8.25
2
1
22
23
24
,N ,N ,N ]p h en yl]et h yn yl]-5-(1,1-d im et h ylet h yl)-
(
8
4
AA′XX′, J AX ) 8.5, 4H), 7.97 and 8.27 (AA′XX′, J AX ) 8.5, 4H),
p h en yl]et h yn yl]p h en yl]-15-[4-[[3-(1,1-d im et h ylet h yl)-5-
iod op h en yl]et h yn yl]p h en yl]-10,20-b is(2,4,6-t r im et h yl-
.70 and 8.76 (2 × d, J ) 4.8, 4H), 8.73 and 8.83 (2 × d, J )
.8, 4H), 8.80 and 8.91 (2 × d, J ) 4.4, 4H), 8.81 and 8.92 (2
p h en yl)-21H,23H-p or p h in a to(4-)-N21,N ,N , N ]](zin c)-
22
23
24
×
2 2
d, J ) 4.4, 4H); UV/vis (CH Cl ) 292 (5.02), 422 (5.95), 516
+
n ick el (8c). Reaction of 7c (210 mg, 102.6 µmol), as described
(
3
4.45), 550 (4.59), 590 (4.19), 650 (3.95); ES -MS (CHCl /
+
2+
for 5a , with subsequent purification by FC (CHCl
Et
N 50:50:0.1), afforded 208 mg (98%) of 8c: 1H NMR (360.14
MHz, CDCl ) δ 0.35 (s, 9H), 1.38 (s, 9H), 1.47 (s, 9H), 1.81 (s,
2H), 1.84 (s, 12H), 2.58 (s, 6H), 2.64 (s, 6H), 7.21 (s, 4H), 7.29
(s, 4H), 7.66 (t J ) 1.5, 1H), 7.72 (t, J ) 1.5, 1H), 7.74 (t, J )
3
/hexane/
MeOH) m/z 1991.9 ([M + H] ), 996.2 ([M + 2H] ) (calcd
average mass for C135 11SiZn 1990.98).
µ-[5-[4-[[3-[[4-[10,20-Bis(2,4,6-tr im eth ylp h en yl)-15-[4-
(tr im eth ylsilyl)eth yn yl]p h en yl]-21H,23H-p or p h in -5-yl-
3
H
121
N
3
[
1
[
N
2
1
22
23
24
,N ,N ,N ]p h en yl]et h yn yl]-5-(1,1-d im et h yl-et h yl)-
1
8
8
.5, 1H), 7.75 (t, J ) 1.5, 1H), 7.79 and 7.99 (AA′XX′, J AX
.2, 4H), 7.81 (t, J ) 1.5, 1H), 7.86 (t, J ) 1.5, 1H), 7.91 and
.07 (AA′XX′, J AX ) 8.2, 4H), 7.92 and 8.24 (AA′XX′, J AX
)
ph en yl]eth yn yl]ph en yl]-15-[4-[[3-(3,3-dieth yl-1-tr iazen yl)-
-(1,1-d im e t h y le t h y l)p h e n y l]e t h y n y l]p h e n y l]-10,20-
b is(2,4,6-t r im e t h ylp h e n yl)-21H ,23H -p or p h in a t o(4-)-
5
)
2
1
22
23
24
8.2, 4H), 7.97 and 8.26 (AA′XX′, J AX ) 8.2, 4H), 8.60 and 8.66
2 × d, J ) 4.8, 4H), 8.62 and 8.73 (2 × d, J ) 4.8, 4H), 8.80
and 8.89 (2 × d, J ) 4.8, 4H), 8.81 and 8.92 (2 × d, J ) 4.8,
H); UV/vis (CH Cl ) 291 (4.96), 422 (5.84), 531 (4.40), 548
(4.49), 590 (3.86); MALDI-MS (dithranol) m/z 2074.4 (M )
calcd average mass for C131 NiSiZn 2074.43).
N
0
,N ,N ,N ]](zin c)n ick el (7c). Reaction of 5c (0.206 g,
.182 mmol) with 6 (0.195 g, 0.187 mmol) in the presence of
Pd(PPh (42.6 mg, 0.043 mmol) in 132 mL of DMF/Et N, as
described for 7a , with subsequent purification by FC (CHCl
N 70:30:0.2), afforded 0.366 g (98%) of 7c: 1H NMR
hexane/Et
360.14 MHz, CDCl ) δ 0.35 (s, 9H), 1.32 (t, J ) 7.4, 6H), 1.42
s, 9H), 1.47 (s, 9H), 1.81 (s, 12H), 1.84 (s, 12H), 2.58 (s, 6H),
(
3
)
4
3
4
2
2
3
/
+
3
(
H109IN
8
(
(
3
[µ-[5-[4-[[5-(1,1-Dim et h ylet h yl)-3-[[4-[15-[4-[[3-(3,3-d i-
eth yl-1-tr ia zen yl)-5-(1,1-d im eth yleth yl)p h en yl]eth yn yl]-
2
7
7
7
7
J
8
8
4
.64 (s, 6H), 3.82 (q, J ) 7.4, 4H), 7.22 (s, 4H), 7.29 (s, 4H),
.49 (d J ) 1.5, 2H), 7.59 (t, J ) 1.5, 1H), 7.72 (t, J ) 1.5, 1H),
.74 (t, J ) 1.5, 1H), 7.79 and 7.99 (AA′XX′, J AX ) 8.5, 4H),
.81 (t, J ) 1.5, 1H), 7.90 and 8.07 (AA′XX′, J AX ) 8.5, 4H),
.93 and 8.22 (AA′XX′, J AX ) 8.5, 4H), 7.97 and 8.26 (AA′XX′,
AX ) 8.5, 4H), 8.60 and 8.67 (2 × d, J ) 4.8, 4H), 8.62 and
.74 (2 × d, J ) 4.8, 4H), 8.80 and 8.91 (2 × d, J ) 4.6, 4H),
ph en yl]-10,20-bis(2,4,6-tr im eth ylph en yl)-21H,23H-por ph in -
5-yl-N 21,N ,N ,N ]p h e n yl]e t h yn yl]p h e n yl]e t h yn yl]-
22
23
24
p h en yl]-15-(4 -et h yn ylp h en yl)-10,20-b is(2,4,6-t r im et h -
ylph en yl)-21H,23H-por ph in ato(4-)-N21, N ,N ,N ]]dizin c
22
23
24
(9a ). Reaction of 7a (348 mg, 0.169 mmol), as described for 6,
with subsequent purification by FC (CHCl
40:0.1), afforded 311 mg (93%) of 9a : 1H NMR (360.14 MHz,
CDCl ) δ 1.32 (t, J ) 7.1, 6H), 1.42 (s, 9H), 1.49 (s, 9H), 1.84
3 3
/hexane/Et N 60:
.81 and 8.92 (2 × d, J ) 4.6, 4H); UV/vis (CH
2 2
Cl ) 292 (5.00),
22 (5.81), 531 (4.40), 548 (4.45), 590 (3.87); ES -MS (THF/
+
3
2
+
HCOOH) m/z 1024.6 ([M + 2H] ) (calcd average mass for
11NiSiZn 2047.66).
µ-[5-[4-[[3-[[4-[10,20-Bis(2,4,6-tr im eth ylp h en yl)-15-[4-
(tr im eth ylsilyl)eth yn yl]p h en yl]-21H,23H-p or p h in -5-yl-
(2 × s, 2 × 12H), 2.64 (s, 12H), 3.30 (s, 1H), 3.82 (q, J ) 7.1,
4H), 7.29 (s, 8H), 7.49 (d J ) 1.5, 2H), 7.59 (t, J ) 1.5, 1H),
7.75 (d, J ) 1.5, 2H), 7.84 (t, J ) 1.5, 1H), 7.88 and 8.21
(AA′XX′, J AX ) 8.2, 4H), 7.93 and 8.22 (AA′XX′, J AX ) 8.2, 4H),
7.98 and 8.26 (AA′XX′, J AX ) 8.2, 4H), 7.98 and 8.27 (AA′XX′,
C
135 119
H N
[
[
N
2
1
22
23
24
,N ,N ,N ]p h en yl]et h yn yl]-5-(1,1-d im et h ylet h yl)-
p h en yl]et h yn yl]p h en yl]-15-[4-[[3-(1,1-d im et h ylet h yl)-5-
iod op h en yl]et h yn yl]p h en yl]-10,20-b is(2,4,6-t r im et h yl-
p h en yl)-21H,23H-p or p h in a to(4-)-N ,N ,N , N ]]d izin c
(
J
AX ) 8.2, 4H), 8.78 and 8.85 (2 × d, J ) 4.6, 4H), 8.79 and
8.90 (2 × d, J ) 4.6, 4H), 8.80 and 8.91 (2 × d, J ) 4.6, 4H),
2
1
22
23
24
8.81 and 8.91 (2 × d, J ) 4.6, 4H); UV/vis (CH
2
Cl
2
) 294 (5.00),
/MeOH) m/z
+
8a ). Reaction of 7a (189 mg, 0.092 mmol), as described for
422 (5.96), 550 (4.64), 590 (3.88); ES -MS (CHCl
3

Supramolecular Assemblies
J . Org. Chem., Vol. 66, No. 15, 2001 4983
+
+ H]2+) (calcd average mass
9
91.0 (M2 ), 940.9 ([M - N
3
Et
2
8.92 (2 × d, J ) 4.6, 4H), 8.81 and 8.93 (2 × d, J ) 4.6, 4H),
for C132
H
111
N
11Zn
2
1982.16).
8.82 and 8.93 (2 × d, J ) 4.8, 16H); UV/vis (CH
2 2
Cl ) 290 (5.31),
+
[
5-[4-[[5-(1,1-Dim eth yleth yl)-3-[[4-[15-[4-[[3-(3,3-dieth yl-
-tr iazen yl)-5-(1,1-dim eth yleth yl)ph en yl]eth yn yl]ph en yl]-
422 (6.22), 550 (4.98), 592 (4.36); ES -MS (CHCl
3
/MeOH) m/z
+
4+
1
1
N
1
2
0
1320.4 (M3 ), 990.4 (M ) (calcd average mass for C259
SiZn 3962.12).
P or p h yr in Tetr a m er 10c. Reaction of 8b (37.2 mg, 18.44
µmol) with 9b (34.4 mg, 17.9 µmol) in the presence of Pd(PPh
(3.1 mg, 2.68 µmol) in 9 mL of DMF/Et N, as described for 7a ,
with subsequent purification by FC (CHCl /hexane/Et N 60:
40:0.2), afforded 62.4 mg (91%) of 10c: 1H NMR (360.14 MHz,
CDCl ) δ -2.63 (s, 2H), -2.60 (s, 2H), 0.37 (s, 9H), 1.32 (t, J
H209IN16-
0,20-b is(2,4,6-t r im et h ylp h en yl)-21H ,23H -p or p h in -5-yl-
4
2
1
22
23
24
,N ,N ,N ]p h en yl]eth yn yl]p h en yl]eth yn yl]p h en yl]-
5-(4-et h yn ylp h en yl)-10,20-b is(2,4,6-t r im et h ylp h en yl)-
1H,23H-p or p h in a to(2-)]zin c (9b). Reaction of 7b (231 mg,
.116 mmol), as described for 6, with subsequent purification
3 4
)
3
3
3
by FC (CHCl
3
/hexane/Et
of 9b: H NMR (360.14 MHz, CDCl
J ) 7.3, 6H), 1.42 (s, 9H), 1.49 (s, 9H), 1.84 (s, 24H), 2.64 (s,
2H), 3.32 (s, 1H), 3.82 (q, J ) 7.3, 4H), 7.29 (s, 8H), 7.49 (d
J ) 1.5, 2H), 7.59 (t, J ) 1.5, 1H), 7.75 (d, J ) 1.5, 2H), 7.84
t, J ) 1.5, 1H), 7.88 and 8.19 (AA′XX′, J AX ) 8.5, 4H), 7.93
and 8.23 (AA′XX′, J AX ) 8.5, 4H), 7.97 and 8.25 (AA′XX′, J AX
8.5, 4H), 7.97 and 8.27 (AA′XX′, J AX ) 8.5, 4H), 8.71 and
3
N 60:40:0.2), afforded 219 mg (98%)
1
3
) δ -2.63 (s, 2H), 1.32 (t,
3
) 7.4, 6H), 1.42 (s, 9H), 1.49 (s, 27H), 1.85 (m, 48H), 2.64 (s,
24H), 3.82 (q, J ) 7.4, 4H), 7.29 (s, 8H), 7.30 (s, 8H), 7.49 (d,
J ) 1.7, 2H), 7.59 (t, J ) 1.7, 1H), 7.76 (d, J ) 1.7, 6H), 7.85
(m, 3H), 7.86 and 8.17 (AA′XX′, J AX ) 8.3, 4H), 7.93 and 8.23
(AA′XX′, J AX ) 8.3, 4H), 7.98 and 8.26 (AA′XX′, J AX ) 8.3, 12H),
7.98 and 8.27 (AA′XX′, J AX ) 8.3, 12H), 8.71 and 8.76 (2 × d,
J ) 4.8, 4H), 8.72 and 8.85 (2 × d, J ) 4.8, 4H), 8.74 and 8.85
(2 × d, J ) 4.8, 8H), 8.81 and 8.91 (2 × d, J ) 4.8, 4H), 8.82
and 8.93 (2 × d, J ) 4.8, 4H), 8.83 and 8.93 (2 × d, J ) 4.8,
1
(
)
8
8
4
.77 (2 × d, J ) 4.8, 4H), 8.73 and 8.83 (2 × d, J ) 4.8, 4H),
.80 and 8.91 (2 × d, J ) 4.4, 4H), 8.81 and 8.92 (2 × d, J )
2 2
.4, 4H); UV/vis (CH Cl ) 292 (4.95), 422 (5.92), 516 (4.34), 550
+
(
1
C
4.52), 590 (4.10), 646 (3.74); ES -MS (CHCl
3
/MeOH) m/z
919.5 ([M + H] ), 956.0 ([M + 2H] ) (calcd average mass for
11Zn 1918.80).
8H); UV/vis (CH
2 2
Cl ) 292 (5.18), 422 (6.18), 516 (4.63), 550
+
2+
+
(4.81), 592 (4.41), 648 (4.25); ES -MS (CHCl /MeOH) m/z
3
H
113
N
1269.9 (M3 ), 1236.8 ([M - N
+
3 2
Et
+ H] ), 952.4 (M ) (calcd
3+
4+
132
[
µ-[5-[4-[[5-(1,1-Dim et h ylet h yl)-3-[[4-[15-[4-[[3-(3,3-d i-
eth yl-1-tr ia zen yl)-5-(1,1-d im eth yleth yl)p h en yl]eth yn yl]-
ph en yl]-10,20-bis(2,4,6-tr im eth ylph en yl)-21H,23H-por ph in -
-yl-N ,N ,N ,N ]p h e n yl]e t h yn yl]p h e n yl]e t h yn yl]-
average mass for C263 19SiZn 3808.63).
H
223
N
2
P or p h yr in Tetr a m er 10d . Reaction of 10c (57.9 mg, 15.2
µmol), as described for 5a , with subsequent purification by FC
2
1
22
23
24
5
(CHCl
3
/hexane/Et
3
N 60:40:0.1), afforded 30.7 mg (53%) of
) δ -2.63 (s, 2H), -2.60 (s,
p h en yl]-15-(4-et h yn ylp h en yl)-10,20-b is(2,4,6-t r im et h yl-
10d : 1H NMR (360.14 MHz, CDCl
3
2
1
22
23
24
p h en yl)-21H,23H-p or p h in a to(4-)-N ,N , N ,N ]](zin c)-
n ick el (9c). Reaction of 7c (350 mg, 170.9 µmol), as described
for 6, with subsequent purification by FC (CHCl
0:50:0.2), afforded 324 mg (96%) of 9c: H NMR (360.14 MHz,
) δ 1.32 (t, J ) 7.4, 6H), 1.42 (s, 9H), 1.47 (s, 9H), 1.81
s, 12H), 1.84 (s, 12H), 2.58 (s, 6H), 2.64 (s, 6H), 3.28 (s, 1H),
2H), 0.37 (s, 9H), 1.38 (s, 9H), 1.49 (s, 27H), 1.85 (m, 48H),
2.64 (s, 24H), 7.30 (2 × s, 16H), 7.66 (t, J ) 1.4, 1H), 7.75 (t,
J ) 1.4, 1H), 7.76 (d, J ) 1.4, 6H), 7.85 (m, 3H), 7.86 (t, J )
1.4, 1H), 7.86 and 8.17 (AA′XX′, J AX ) 8.2, 4H), 7.92 and 8.24
(AA′XX′, J AX ) 8.2, 4H), 7.98 (apparent d, J ) 8.4, 12H), 8.26
(m, 6H), 8.27 (m, 6H), 8.71 and 8.76 (2 × d, J ) 4.8, 4H), 8.72
and 8.85 (2 × d, J ) 4.8, 4H), 8.74 and 8.85 (2 × d, J ) 4.8,
8H), 8.81 and 8.90 (2 × d, J ) 4.8, 4H), 8.818 and 8.929 (2 ×
d, J ) 4.8, 4H), 8.824 and 8.933 (2 × d, J ) 4.8, 8H); UV/vis
3
/hexane/Et
3
N
1
5
CDCl
(
3
2
1
8
(
8
4
3
.82 (q, J ) 7.4, 4H), 7.22 (s, 4H), 7.29 (s, 4H), 7.49 (d J ) 1.5,
H), 7.59 (t, J ) 1.5, 1H), 7.72 (t, J ) 1.5, 1H), 7.74 (t, J )
.5, 1H), 7.81 (t, J ) 1.5, 1H), 7.81 and 8.01 (AA′XX′, J AX
)
.5, 4H), 7.90 and 8.07 (AA′XX′, J AX ) 8.5, 4H), 7.93 and 8.23
(CH
2 2
Cl ) 292 (5.14), 422 (6.15), 516 (4.62), 550 (4.76), 592
+
AA′XX′, J AX ) 8.5, 4H), 7.97 and 8.26 (AA′XX′, J AX ) 8.5, 4H),
(4.32), 648 (4.10); ES -MS (CHCl /MeOH/HCOOH) m/z 1918.1
3
3+
([M + 2H]2 ), 1279.2 ([M + 3H] ), 1258.2 ([M - Zn + 5H] ),
+
3+
.60 and 8.68 (2 × d, J ) 4.8, 4H), 8.62 and 8.74 (2 × d, J )
3
+
4+
.8, 4H), 8.80 and 8.91 (2 × d, J ) 4.8, 4H), 8.81 and 8.92 (2
1237.1 ([M - 2Zn + 7H] ), 959.6 ([M + 4H] ), 943.9 ([M -
4
+
4+
×
d, J ) 4.8, 4H); UV/vis (CH
2
Cl
2
) 292 (4.99), 422 (5.80), 530
Zn + 6H] ), 928.2 ([M - 2Zn + 8H] ), 755.4 ([M - Zn +
7H]5 ), 742.6 ([M - 2Zn + 9H] ) (calcd average mass for
3835.39).
P or p h yr in Tetr a m er 10e. Reaction of 8c (180 mg, 86.8
µmol) with 9c (176.6 mg, 89.4 µmol) in the presence of Pd-
(PPh (15 mg, 13 µmol) in 45 mL of DMF/Et N, as described
3
for 7a , with subsequent purification by 2-fold FC (CHCl /
+
5+
(
4.39), 548 (4.45), 590 (3.87); MALDI-MS (dithranol) m/z 1876.2
+
(
1
[M - N
975.48).
P or p h yr in Tetr a m er 10a . Reaction of 8a (58.8 mg, 28.3
µmol) with 9a (54.2 mg, 27.3 µmol) in the presence of Pd(PPh
N, as described for
a , with subsequent purification by FC (CHCl /hexane/Et
0:40:0.2), afforded 88.4 mg (82%) of 10a : H NMR (360.14
) δ 0.38 (s, 9H), 1.32 (t, J ) 7.2, 6H), 1.42 (s, 9H),
3
Et
2
] ) (calcd average mass for C132
H
111
N
11NiZn
259 2
C H213IN16SiZn
3
)
4
3
)
4
3
(
7
6
4.8 mg, 4.15 µmol) in 13.2 mL of DMF/Et
3
1
3
3
N
hexane/Et
3
N 60:40:0.2), afforded 204 mg (60%) of 10e:
H
1
NMR (500.13 MHz, CDCl
3
) δ 0.35 (s, 9H), 1.32 (t, J ) 7.4, 6H),
MHz, CDCl
3
1.42 (s, 9H), 1.47 (s, 27H), 1.81 (s, 12H), 1.83 (s, 12H), 1.85 (s,
24H), 2.58 (2 × s, 2 × 6H), 2.64 (s, 12H), 3.82 (q, J ) 7.4, 4H),
7.21 (s, 4H), 7.23 (s, 4H), 7.29 (s, 8H), 7.49 (d, J ) 1.5, 2H),
7.59 (t, J ) 1.5, 1H), 7.72 (m, 3H), 7.74 (m, 3H), 7.78 and 7.99
(AA′XX′, J AX ) 8.2, 4H), 7.81 (m, 3H), 7.90 and 8.07 (AA′XX′,
1
2
7
(
(
7
J
8
8
4
.49 (s, 27H), 1.84 (2 × s, 24H), 1.85 (s, 24H), 2.64 (s, 12H),
.65 (s, 12H), 3.80 (q, J ) 7.2, 4H), 7.29 (s, 8H), 7.30 (s, 8H),
.49 (d, J ) 1.6, 2H), 7.59 (t, J ) 1.6, 1H), 7.76 (m, 6H), 7.84
m, 3H), 7.86 and 8.18 (AA′XX′, J AX ) 8.2, 4H), 7.93 and 8.23
AA′XX′, J AX ) 8.2, 4H), 7.98 and 8.26 (AA′XX′, J AX ) 8.1, 4H),
J
AX ) 8.2, 4H), 7.91 and 8.08 (AA′XX′, J AX ) 8.2, 8H), 7.93
.98 and 8.27 (AA′XX′, J AX ) 8.1, 4H), 7.98 and 8.28 (AA′XX′,
AX ) 8.2, 16H), 8.79 and 8.85 (2 × d, J ) 4.6, 4H), 8.80 and
.91 (2 × d, J ) 4.6, 4H), 8.80 and 8.92 (2 × d, J ) 4.6, 4H),
.81 and 8.92 (2 × d, J ) 4.6, 4H), 8.82 and 8.93 (2 × d, J )
and 8.23 (AA′XX′, J AX ) 8.2, 4H), 7.97 and 8.26 (AA′XX′, J AX
) 8.5, 12H), 8.60 and 8.66 (2 × d, J ) 4.8, 4H), 8.62 and 8.73
(2 × d, J ) 4.8, 4H), 8.63 and 8.74 (2 × d, J ) 4.8, 8H), 8.80
and 8.91 (2 × d, J ) 4.8, 4H), 8.81 and 8.92 (2 × d, J ) 4.8,
.8, 16H); UV/vis (CH
2
+
Cl
2
) 294 (5.13), 422 (6.19), 550
4H), 8.82 and 8.92 (2 × d, J ) 4.8, 8H); UV/vis (CH
2 2
Cl ) 291
(
4.95), 584 (4.76); ES -MS (CHCl
3
/MeOH) m/z 1311.6
), 983.6 (M ) (calcd average mass for C263 19SiZn
935.36).
P or p h yr in tetr a m er 10b. Reaction of 10a (40.5 mg, 10.3
µmol), as described for 5a , with subsequent purification by FC
CHCl /hexane/Et N, gradient from 55:45:0.1 to 70:30:0.1),
afforded 34.8 mg (85%) of 10b: H NMR (360.14 MHz, CDCl
(5.48), 422 (6.29), 533 (4.87), 548 (4.94), 590 (4.30); MALDI-
3
+
4+
+
2
(M
H
219
N
4
MS (dithranol) m/z 3822.4 ([M - N
3
Et ] ) (calcd average mass
3
for C263
H
219
N
19Ni
2
SiZn 3922.00).
2
P or p h yr in Tetr a m er 10f. Reaction of 10e (204 mg, 52
µmol), as described for 5a , with subsequent purification by FC
(
3
3
(CHCl
3 3
/hexane/Et N, gradient from 60:40:0.1 to 70:30:0.1),
1
1
3
)
afforded 161 mg (78%) of 10f: H NMR (360.14 MHz, CDCl )
3
δ 0.38 (s, 9H), 1.38 (s, 9H), 1.49 (s, 27H), 1.84 (2 × s, 24H),
δ 0.35 (s, 9H), 1.38 (s, 9H), 1.47 (s, 27H), 1.81 (s, 12H), 1.83
(s, 12H), 1.84 (s, 12H), 1.85 (s, 12H), 2.58 (2 × s, 2 × 6H), 2.64
(s, 12H), 7.21 (s, 4H), 7.23 (s, 4H), 7.29 (s, 8H), 7.66 (t, J )
1.5, 1H), 7.73 (m, 3H), 7.74 (t, J ) 1.5, 1H), 7.74 (m, 3H), 7.78
and 7.99 (AA′XX′, J AX ) 8.2, 4H), 7.81 (m, 3H), 7.86 (t, J )
1.5, 1H), 7.90 and 8.07 (AA′XX′, J AX ) 8.2, 4H), 7.91 and 8.08
(AA′XX′, J AX ) 8.2, 8H), 7.92 and 8.24 (AA′XX′, J AX ) 8.2, 4H),
1
8
7
.85 (s, 24H), 2.64 (s, 12H), 2.65 (s, 12H), 7.29 (s, 8H), 7.30 (s,
H), 7.66 (t, J ) 1.5, 1H), 7.75 (t, J ) 1.5, 1H), 7.76 (m, 6H),
.84 (m, 3H), 7.86 (t, J ) 1.5, 1H), 7.86 and 8.18 (AA′XX′, J AX
)
8.2, 4H), 7.92 and 8.24 (AA′XX′, J AX ) 8.3, 4H), 7.98
apparent d, J ) 8.1, 12H), 8.27 (m, 12H), 8.78 and 8.85 (2 ×
d, J ) 4.6, 4H), 8.80 and 8.89 (2 × d, J ) 4.7, 4H), 8.80 and
(

4
984 J . Org. Chem., Vol. 66, No. 15, 2001
Rucareanu et al.
7
.97 and 8.26 (AA′XX′, J AX ) 8.2, 12H), 8.60 and 8.66 (2 × d,
(2 × d, J ) 4.8, 4H), 8.73 and 8.85 (2 × d, J ) 4.8, 4H), 8.74
and 8.85 (2 × d, J ) 4.8, 16H), 8.81 and 8.89 (2 × d, J ) 4.6,
4H), 8.82 and 8.92 (2 × d, J ) 4.8, 4H), 8.82 and 8.93 (2 × d,
J ) 4.8, 4H), 8.62 and 8.73 (2 × d, J ) 4.8, 4H), 8.63 and 8.74
(
2 × d, J ) 4.8, 8H), 8.80 and 8.89 (2 × d, J ) 4.8, 4H), 8.81
and 8.92 (2 × d, J ) 4.8, 4H), 8.82 and 8.92 (2 × d, J ) 4.8,
H); UV/vis (CH Cl ) 290 (5.32), 422 (6.16), 532 (4.74), 549
4.82), 591 (4.21); MALDI-MS (dithranol) m/z 3948.6 (M )
calcd average mass for C259 SiZn 3948.76).
Lin ea r P or p h yr in Hexa m er 11a . Reaction of 10b (33.0
mg, 8.33 µmol) with 9a (16.0 mg, 8.07 µmol) in the presence
of Pd(PPh (1.44 mg, 1.25 µmol) in 4.08 mL of DMF/Et N, as
described for 7a , with subsequent purification by FC (CHCl
hexane/Et N, gradient from 60:40:0.2 to 70:30:0.2), afforded
8.3 mg (82%) of 11a : H NMR (360.14 MHz, CDCl
s, 9H), 1.32 (t, J ) 7.2, 6H), 1.42 (s, 9H), 1.49 (s, 45H), 1.83,
2 2
J ) 4.8, 16H); UV/vis (CH Cl ) 292 (5.32), 422 (6.31), 516 (4.76),
+
8
(
(
2
2
550 (4.92), 590 (4.47), 646 (4.14); ES -MS (THF/HCOOH) m/z
+
4+
4+
1396.1 ([M + 4H] ), 1380.4 ([M - Zn + 6H] ), 1117.1 ([M +
5H]5 ), 1104.5 ([M - Zn + 7H] ) (calcd average mass for
5580.85).
Lin ea r P or p h yr in Hexa m er 11e. Reaction of 10b (23.3
mg, 5.88 µmol) with 9b (11.7 mg, 6.10 µmol) in the presence
of Pd(PPh (1.0 mg, 0.88 µmol) in 2.7 mL of DMF/Et N, as
described for 7a , with subsequent purification by FC (CHCl
hexane/Et N 60:40:0.2 then 70:30:0.2), afforded 28.8 mg (85%)
of 11e: H NMR (360.14 MHz, CDCl ) δ -2.60 (s, 2H), 0.37
+
5+
H
209IN16Ni
2
2
C
384 3
H307IN24Zn
3
)
4
3
3
/
3
)
4
3
3
3
/
1
3
(
1
3
) δ 0.38
3
1
3
.84 and 1.85 (3 × s, 12H, 12H and 48H), 2.63 (s, 12H), 2.64
(s, 9H), 1.32 (t, J ) 7.0, 6H), 1.42 (s, 9H), 1.49 (s, 45H), 1.84-
1.86 (m, 72H), 2.64 (s, 36H), 3.82 (q, J ) 7.0, 4H), 7.30 (s, 24H),
7.50 (d, J ) 1.8, 2H), 7.59 (t, J ) 1.8, 1H), 7.76 (m, 10H), 7.85
(m, 5H), 7.86 and 8.18 (AA′XX′, J AX ) 8.3, 4H), 7.93 and 8.23
(AA′XX′, J AX ) 8.3, 4H), 7.98 and 8.27 (2 × AA′XX′, J AX ) 8.3,
8H), 7.98 and 8.28 (AA′XX′, J AX ) 8.3, 32H), 8.74 and 8.85 (2
× d, J ) 4.8, 8H), 8.79 and 8.86 (2 × d, J ) 4.8, 4H), 8.81 and
8.91 (2 × d, J ) 4.4, 4H), 8.81 and 8.92 (2 × d, J ) 4.4, 4H),
8.82 and 8.92 (2 × d, J ) 4.4, 4H), 8.82 and 8.93 (2 × d, J )
(
s, 24H), 3.81 (q, J ) 7.2, 4H), 7.29 (s, 8H), 7.30 (s, 16H), 7.49
(d, J ) 1.5, 2H), 7.59 (t, J ) 1.5, 1H), 7.76 (d, J ) 1.5, 10H),
7
7
8
8
4
.85 (t, J ) 1.5, 5H), 7.86 and 8.18 (AA′XX′, J AX ) 8.4, 4H),
.93 and 8.23 (AA′XX′, J AX ) 8.3, 4H), 7.97-7.99 (m, 20H),
.26, 8.27 and 8.28 (3 × apparent d, J ) 8.3, 2H, 2H and 16H),
.79 and 8.85 (2 × d, J ) 4.6, 4H), 8.80 and 8.91 (2 × d, J )
.6, 4H), 8.81 and 8.92 (2 × d, J ) 4.6, 4H), 8.82 and 8.93 (2
×
d, J ) 4.6, 4H), 8.82 and 8.94 (2 × d, J ) 4.7, 32H); UV/vis
+
(CH
2
Cl
3
2
) 294 (5.37), 422 (6.29), 550 (5.04), 590 (4.44); ES -MS
4.8, 24H); UV/vis (CH
550 (5.19), 592 (4.72), 648 (4.39); ES -MS (CHCl /MeOH) m/z
2 2
Cl ) 290 (5.58), 422 (6.42), 516 (4.79),
+ 17H]4 ),
+
+
(CHCl
/MeOH/HCOOH) 1335.2 ([M - 6Zn - N
3
Et
2
3
5
+
3+
4+
1
068.2 ([M - 6Zn - N
3
Et
+ 19H] ), 763.3 ([M - 6Zn - N
27SiZn 5816.37).
Lin ea r P or p h yr in Hexa m er 11b. Reaction of 11a (37.5
mg, 6.45 µmol) with CH I, as described for 5a (72%), followed
by treatment with NaOH, as described for 6 (88%), afforded
2
+ 18H] ), 890.5 ([M - 6Zn - N
3
-
1884.4 ([M - N
average mass for C391
Lin ea r P or p h yr in Hexa m er 11f. Reaction of 11e (14.5
mg, 2.52 µmol) with CH I, as described for 5a (62%), followed
by treatment with NaOH, as described for 6 (75%), afforded
6.7 mg of 11f: 1H NMR (360.14 MHz, CDCl
) δ -2.60 (s, 2H),
3
Et
2
+ H] ), 1413.6 ([M - N
H
3 2
Et + H] ) (calcd
6
+
7+
Et
2
3
Et
2
+ 20H] ) (calcd
321
N
27SiZn 5753.00).
5
average mass for C391
H
319
N
6
3
3
3
1
2
1
3.6 mg of 11b: H NMR (500.13 MHz, CDCl
3
) δ 1.38 (s, 9H),
1.38 (s, 9H), 1.49 (s, 45H), 1.84 and 1.85 (2 × s, 72H), 2.64 (s,
36H), 3.31 (s, 1H), 7.30 (s, 24H), 7.66 (t, J ) 1.4, 1H), 7.76 (m,
11H), 7.85 (m, 5H), 7.87 (t, J ) 1.4, 1H), 7.88 and 8.20 (AA′XX′,
.49 (s, 45H), 1.84 (2 s, 24H), 1.85 (s, 48H), 2.64 (s, 12H), 2.65
(s, 24H), 3.31 (s, 1H), 7.29 (s, 8H), 7.30 (s, 16H), 7.66 (t, J )
1
5
4
8
8
4
.5, 1H), 7.75 (t, J ) 1.6, 1H), 7.76 (d, J ) 1.5, 10H), 7.85 (m,
H), 7.86 (t, J ) 1.5, 1H), 7.88 and 8.21 (AA′XX′, J AX ) 8.3,
H), 7.92 and 8.24 (AA′XX′, J AX ) 8.3, 4H), 7.97-7.99 (m, 20H),
.26, 8.27 and 8.28 (3 × apparent d, J ) 8.3, 2H, 2H and 16H),
.79 and 8.86 (2 × d, J ) 4.6, 4H), 8.80 and 8.90 (2 × d, J )
.6, 4H), 8.81 and 8.92 (2 × d, J ) 4.7, 4H), 8.81 and 8.93 (2
J AX ) 8.1, 4H), 7.92 and 8.24 (AA′XX′, J AX ) 8.1, 4H), 7.98
(apparent d, J ) 8.1, 20H), 8.28 (m, 20H), 8.74 and 8.85 (2 ×
d, J ) 4.8, 8H), 8.80 and 8.86 (2 × d, J ) 4.8, 4H), 8.81 and
8.90 (2 × d, J ) 4.4, 4H), 8.81 and 8.93 (2 × d, J ) 4.4, 8H),
8.82 and 8.93 (2 × d, J ) 4.4, 24H); UV/vis (CH
2 2
Cl ) 294 (5.42),
+
422 (6.38), 516 (4.59), 550 (5.08), 588 (4.58), 650 (4.21); ES -
3
+
×
d, J ) 4.7, 4H), 8.82 and 8.94 (2 × d, J ) 4.6, 32H); UV/vis
3
MS (CHCl /MeOH/HCOOH) m/z 1797.9 ([M - 5Zn + 13H] ),
+
4+
5+
(CH
2
Cl
3
2
) 290 (5.38), 422 (6.38), 550 (5.09), 590 (4.30); ES -MS
1348.7 ([M - 5Zn + 14H] ), 1079.1 ([M - 5Zn + 15H] ), 899.4
4
+
6+
(CHCl
/MeOH/HCOOH) m/z 1348.7 ([M - 6Zn + 16H] ),
([M - 5Zn + 16H] ) (calcd average mass for C384H303IN24Zn
5
5
+
6+
1
079.1 ([M - 6Zn + 17H] ), 899.5 ([M - 6Zn + 18H] ), 771.1
5707.58).
7
+
(
[M - 6Zn + 19H] ) (calcd average mass for C384
770.95).
Lin ea r P or p h yr in Hexa m er 11c. Reaction of 10d (81.2
mg, 21.2 µmol) with 9b (41.8 mg, 21.8 µmol) in the presence
of Pd(PPh (3.7 mg, 3.2 µmol) in 9.0 mL of DMF/Et N, as
described for 7a , with subsequent purification by FC (CHCl
H
301IN24Zn
6
Lin ea r P or p h yr in Hexa m er 11g. Reaction of 10f (160 mg,
40.5 µmol) with 9c (83.0 mg, 42 µmol) in the presence of Pd-
5
(PPh
described for 7a , with subsequent purification by 2-fold FC
(CHCl /hexane/Et N, gradient from 50:50:0.2 to 70:30:0.2),
3
afforded 143 mg (61%) of 11g: H NMR (360.14 MHz, CDCl )
3
)
4
(7.1 mg, 6.1 µmol) in 18.6 mL of DMF/Et
3
N, as
3
)
4
3
3
3
1
3
/
H
1
hexane/Et
NMR (360.14 MHz, CDCl
s, 9H), 1.32 (t, J ) 7.0, 6H), 1.42 (s, 9H), 1.49 (s, 45H), 1.84,
3
N 60:40:0.2), afforded 102.9 mg (86%) of 11c:
δ 0.35 (s, 9H), 1.32 (t, J ) 7.4, 6H), 1.42 (s, 9H), 1.47 (s, 45H),
1.81 and 1.83 (2 × s, 36H), 1.84 and 1.85 (2 × s, 36H), 2.57
and 2.58 (2 × s, 18H), 2.64 (s, 18H), 3.82 (q, J ) 7.4, 4H), 7.21
(s, 4H), 7.22 (s, 8H), 7.29 (s, 12H), 7.49 (d, J ) 1.5, 2H), 7.59
(t, J ) 1.5, 1H), 7.73 (t, J ) 1.5, 5H), 7.74 (t, J ) 1.5, 5H),
7.78 and 7.99 (AA′XX′, J AX ) 8.2, 4H), 7.82 (m, 5H), 7.91 and
8.07 (AA′XX′, J AX ) 8.2, 4H), 7.91 and 8.08 (2 × AA′XX′, J AX
) 8.2, 16H), 7.93 and 8.23 (AA′XX′, J AX ) 8.2, 4H), 7.97 and
8.26 (AA′XX′, J AX ) 8.2, 20H), 8.60 and 8.66 (2 × d, J ) 4.8,
4H), 8.62 and 8.73 (2 × d, J ) 4.8, 4H), 8.63 and 8.74 (2 × d,
J ) 4.8, 16H), 8.80 and 8.91 (2 × d, J ) 4.8, 4H), 8.81 and
8.92 (2 × d, J ) 4.8, 4H), 8.82 and 8.92 (2 × d, J ) 4.8, 16H);
3
) δ -2.63 (s, 2H), -2.60 (s, 4H), 0.38
(
1
7
7
8
8
8
8
4
2
.85 and 1.86 (3 × s, 72H), 2.64 (s, 36H), 3.82 (q, J ) 7.0, 4H),
.30 (s, 24H), 7.49 (d, J ) 1.4, 2H), 7.59 (m, 1H), 7.76 (m, 10H),
.85 (m, 5H), 7.86 and 8.17 (AA′XX′, J AX ) 8.5, 4H), 7.93 and
.23 (AA′XX′, J AX ) 8.5, 4H), 7.98 (apparent d, J ) 8.5, 20H),
.26 (m, 20H), 8.71 and 8.76 (2 × d, J ) 4.8, 4H), 8.72 and
.85 (2 × d, J ) 4.8, 4H), 8.74 and 8.85 (2 × d, J ) 4.8, 16H),
.80 and 8.91 (2 × d, J ) 4.6, 4H), 8.82 and 8.92 (2 × d, J )
.6, 4H), 8.82 and 8.93 (2 × d, J ) 4.7, 16H); UV/vis (CH
2 2
Cl )
94 (5.44), 422 (6.42), 516 (4.88), 550 (5.04), 590 (4.58), 646
+
3+
(
4.26); ES -MS (CHCl
381.8 ([M - N Et + H] ) (calcd average mass for C391
SiZn 5626.27).
Lin ea r P or p h yr in Hexa m er 11d . Reaction of 11c (48.8
mg, 8.67 µmol) with CH I, as described for 5a (43%), followed
by treatment with NaOH, as described for 6 (77%), afforded
3
/MeOH) m/z 1842.3 ([M - N
3
Et
2
+ H] ),
H
UV/vis (CH
2 2
Cl ) 291 (5.59), 423 (6.39), 533 (4.97), 548 (5.05),
4
+
+
1
3
2
325
N
27
-
590 (4.43); MALDI-MS (dithranol) m/z 5696.0 ([M - N
3
Et
3 2
Et + dithranol] ) (calcd average mass for
2
] ),
+
3
5918.1 ([M - N
SiZn
1836.2 ([M - N Et
3Zn + 10H]4 ), 1102.0 ([M - N
Lin ea r P or p h yr in Hexa m er 11h . Reaction of 11g (142
mg, 24.5 µmol) with CH I, as described for 5a (93%), followed
by treatment with NaOH, as described for 6 (94%), afforded
123.4 mg of 11h : 1H NMR (360.14 MHz, CDCl
) δ 1.38 (s, 9H),
+
C
391
H
319
N
27Ni
3
3
5796.33); ES -MS (CHCl
3
/HCOOH) m/z
3
+
3
3
2
- 3Zn + 9H] ), 1377.2 ([M - N Et -
3
2
+
5+
3
2
Et - 3Zn + 11H] ).
1
2
2
1
7
1
3
1.1 mg of 11d : H NMR (360.14 MHz, CDCl ) δ -2.63 (s,
H), -2.60 (s, 4H), 1.38 (s, 9H), 1.49 (s, 45H), 1.84, 1.85 and
.86 (3 × s, 72H), 2.64 (s, 36H), 3.31 (s, 1H), 7.30 (2 × s, 24H),
.66 (t, J ) 1.4, 1H), 7.75 (t, J ) 1.4, 1H), 7.76 (d, J ) 1.4,
0H), 7.85 (d, J ) 1.4, 5H), 7.86 (t, J ) 1.4, 1H), 7.90 and 8.20
3
3
1.49 (s, 45H), 1.81 and 1.83 (2 × s, 36H), 1.84 and 1.85 (2 × s,
36H), 2.57 and 2.58 (2 × s, 18H), 2.63 (s, 18H), 3.26 (s, 1H),
7.21 (s, 4H), 7.22 (s, 8H), 7.29 (s, 12H), 7.66 (t, J ) 1.5, 1H),
(
7
AA′XX′, J AX ) 8.4, 4H), 7.94 and 8.24 (AA′XX′, J AX ) 8.5, 4H),
.98 (apparent d, J ) 8.1, 20H), 8.27 (m, 20H), 8.71 and 8.78

Supramolecular Assemblies
J . Org. Chem., Vol. 66, No. 15, 2001 4985
7
4
J
.73 (m, 5H), 7.74 (m, 6H), 7.81 and 8.01 (AA′XX′, J AX ) 8.2,
H), 7.82 (m, 5H), 7.86 (t, J ) 1.5, 1H), 7.91 and 8.07 (AA′XX′,
AX ) 8.2, 4H), 7.91 and 8.08 (AA′XX′, J AX ) 8.2, 16H), 7.92
TFA (120 µL, 1.52 mmol), according to the general procedure:
1
H NMR (360.14 MHz, CDCl
3
) δ -2.44 (br s, 2H, NH), 0.64 (s,
9H, -(CH
3
)
3
), 0.88 (t, J ) 6.8, 6H, -CH
CH CH CH ), 1.49 (m, 4H, -CH
CH CH CH CH
CH CH
), 8.08 and 9.01 (AA′XX′, J AX
N), 8.70 and 9.34 (2 × d, J ) 5.0, 4H, â-H on
porphine), 9.44 and 9.72 (2 × d, J ) 5.0, 4H, â-H on porphine);
UV/vis (CH Cl ) 426 (5.59), 529 (4.09), 568 (4.32), 608 (3.65),
667 (4.05); ES -MS (THF/HCOOH) m/z 681.00 ([M + H] ).
Anal. Calcd for C44 Si (680.02): C, 77.71; H, 7.86; N,
10.30. Found: C, 77.54; H, 8.01; N, 10.23.
,15-Dip r op yl-10-(4-iod op h en yl)-20-(p yr id -4-yl)-21H ,-
3H-p or p h in e (14a ) was obtained in 6% yield by reacting 12a
3
), 1.32 (m, 8H, -CH
2
-
-
and 8.24 (AA′XX′, J AX ) 8.2, 4H), 7.97 and 8.26 (2 × AA′XX′,
CH
CH
2
CH
CH
2
CH
2
2
2
3
2
CH
2
CH
2
CH
2
CH
2
J
AX ) 8.2, 20H), 8.60 and 8.68 (2 × d, J ) 4.8, 4H), 8.62 and
.74 (2 × d, J ) 4.8, 4H), 8.63 and 8.75 (2 × d, J ) 4.8, 16H),
.80 and 8.90 (2 × d, J ) 4.8, 4H), 8.81 and 8.93 (2 × d, J )
2
3
), 1.75 (m, 4H, -CH
CH CH CH CH
CH CH CH CH
2
2
2
2
2
CH
2
3
CH ), 2.46
8
8
4
2
(m, 4H, -CH
-CH CH CH
6 4
5.9, 4H, -C H
2
2
2
2
2
2
3
), 4.86 (t, J ) 8.0, 4H,
2
2
2
2
2
2
3
)
.8, 4H), 8.82 and 8.93 (2 × d, J ) 4.8, 16H); UV/vis (CH
2
Cl
2
)
90 (5.47), 423 (6.32), 534 (4.87), 548 (4.96), 590 (4.27); MALDI-
+
MS (dithranol) m/z 5751.1 (M ) (calcd average mass for
Zn 5750.91).
Gen er a l P r oced u r e for th e Syn th esis of m eso-Alk yl-
,2′-d ip yr r ylm eth a n es 12a -e. To a solution of pyrrole (200
mmol) and alkyl aldehyde (20 mmol) in CH Cl (300 mL) was
added dropwise a 8 M solution of BF ‚OEt in CH Cl (0.45
2
2
+
+
C
384
H
301IN24Ni
3
3
53 5
H N
2
2
2
5
3
2
2
2
2
mL, 3.6 mmol), and the reaction mixture was allowed to stir
at 20 °C for 3 h. Triethylamine (2 mL) was then added, and
the solvent was removed under reduced pressure. The crude
32
(
188 mg, 1 mmol) with 4-iodobenzaldehyde (232 mg, 1 mmol)
and 4-pyridinecarbaldehyde (96 µL, 1 mmol), according to the
general procedure: 1H NMR (360.14 MHz, CDCl
) δ -2.76 (br
s, 2H, NH), 1.30 (t, J ) 7.3, 6H, -CH ), 2.53 (m, 4H, -CH CH
CH ), 4.92 (t, J ) 7.3, 4H, -CH CH CH ), 7.91 and 8.09
AA′XX′, J AX ) 8.0, 4H, -C I), 8.13 and 9.02 (AA′XX′, J AX
4.0, 4H, -C
3
2 2 3
product was purified by FC (CH Cl /hexane/Et N 2:1:0.01),
3
2
2
-
affording the corresponding dipyrrylmethane as a yellow oil,
which was used without further purification for the synthesis
of the corresponding porphyrins.
3
2
2
3
(
6 4
H
)
6
H
4
N), 8.79 and 9.45 (2 × d, J ) 4.8, 4H, â-H on
1
m eso-P r op yl-2,2′-d ip yr r ylm eth a n e (12a ): 40%; H NMR
porphine), 8.84 and 9.43 (2 × d, 4H, â-H on porphine); UV/vis
(360.14 MHz, CDCl
3
) δ 0.92 (t, J ) 7.3, 3H, CH
3
), 1.31 (m,
), 4.00 (t, J ) 7.6, 1H, CH), 6.06
(CH Cl ) 301 (4.15), 418 (5.54), 516 (4.21), 551 (3.90), 594
2
2
2
H, CH ), 1.92 (m, 2H, CH
2
2
(3.66), 650 (3.72); ES
+
-MS (CHCl /HCOOH) m/z 674.51 ([M +
3
(m, 2H, H-5,5′), 6.13 (m, 2H, H-4, 4′), 6.63 (m, 2H, H-3,3′), 7.82
H]
C, 65.97; H, 4.79; N, 10.40. Found: C, 66.10; H, 4.55; N, 10.24.
,15-Dibu tyl-10-(4-iodoph en yl)-20-(pyr id-4-yl)-21H,23H-
p or p h in e (14b) was obtained in 4% yield after purification
by FC (CH Cl ), reacting 12b (202 mg, 1 mmol) with 4-iodo-
benzaldehyde (232 mg, 1 mmol) and 4-pyridinecarbaldehyde
+
), 337.7 ([M + 2H]2+). Anal. Calcd for C H N I (673.59):
3
7
32
5
(br s, 2H, NH).
1
m eso-Bu tyl-2,2′-d ip yr r ylm eth a n e (12b): 35%; H NMR
5
(
4
(
360.14 MHz, CDCl
H, CH ), 1.93 (m, 2H, CH
m, 2H, H-5, 5′), 6.13 (m, 2H, H-4, 4′), 6.62 (m, 2H, H-3,3′),
3
) δ 0.87 (t, J ) 7.0, 3H, CH
3
), 1.30 (m,
), 3.96 (t, J ) 7.6, 1H, CH), 6.06
2
2
2
2
32
7
.75 (br s, 2H, NH).
1
(
(
6
-
7
(
4
96 µL, 1 mmol), according to the general procedure: H NMR
360.14 MHz, CDCl ) δ -2.75 (br s, 2H, NH), 1.11 (t, J ) 7.7,
H, -CH ), 1.79 (m, 4H, -CH CH CH CH ), 2.49 (m, 4H,
CH CH CH CH ), 4.97 (t, J ) 7.7, 4H, -CH CH CH CH ),
.92 and 8.10 (AA′XX′, J AX ) 8.1, 4H, -C I), 8.15 and 9.03
AA′XX′, J AX ) 5.9, 4H, -C
N), 8.80 and 9.46 (2 × d, J )
.8, 4H, â-H on porphine), 8.85 and 9.44 (2 × d, J ) 4.8, 4H,
Cl ) 303 (4.18), 418 (5.49), 516
4.17), 551 (3.88), 594 (3.59), 651 (3.66); ES -MS (CHCl
m eso-P en tyl-2,2′-d ip yr r ylm eth a n e (12c):11,14 44%; 1H
3
NMR (360.14 MHz, CDCl
3
) δ 0.86 (t, J ) 7.0, 3H, CH
3
), 1.29
3
2
2
2
3
(m, 6H, CH
2
), 1.93 (m, 2H, CH ), 3.97 (t, J ) 7.6, 1H, CH),
2
2
2
2
3
2
2
2
3
6
7
.05 (m, 2H, H-5,5′), 6.14 (m, 2H, H-4, 4′), 6.63 (m, 2H, H-3,3′),
6 4
H
.77 (br s, 2H, NH).
m eso-Hexyl-2,2′-d ip yr r ylm eth a n e (12d ): 32%; H NMR
6 4
H
1
(360.14 MHz, CDCl
3
) δ 0.86 (t, J ) 7.0, 3H, CH
3
), 1.29 (m,
â-H on porphine); UV/vis (CH
(
2
2
8
H, CH
2
), 1.93 (m, 2H, CH ), 3.94 (t, J ) 7.6, 1H, CH), 6.05
2
+
3
/
(
7
m, 2H, H-5, 5′), 6.14 (m, 2H, H-4, 4′), 6.62 (m, 2H, H-3,3′),
.75 (br s, 2H, NH).
m eso-Hep tyl-2,2′-d ip yr r ylm eth a n e (12e): 38%; H NMR
360.14 MHz, CDCl ) δ 0.86 (t, J ) 7.0, 3H, CH ), 1.28 (m,
), 1.93 (m, 2H, CH ), 3.98 (t, J ) 7.6, 1H, CH), 6.06
+
2+
HCOOH) m/z 702.60 ([M + H] ), 351.79 ([M + 2H] ). Anal.
Calcd for C39 I (701.65): C, 66.76; H, 5.17; N, 9.98.
Found: C, 66.54; H, 5.12; N, 10.12.
,15-Dip en t yl-10-(4-iod op h en yl)-20-(p yr id -4-yl)-21H ,-
3H-p or p h in e (14c) was obtained in 5% yield by reacting 12c
216 mg, 1 mmol) with 4-iodobenzaldehyde32 (232 mg, 1 mmol)
and 4-pyridinecarbaldehyde (96 µL, 1 mmol), according to the
general procedure: 1H NMR (360.14 MHz, CDCl
) δ -2.75 (br
), 1.51 (m, 4H, -CH
CH CH CH CH ), 2.50
), 4.94 (t, J ) 8.1, 4H, -CH
), 7.91 and 8.09 (AA′XX′, J AX ) 8.4, 4H,
N), 8.79
36 5
H N
1
(
1
(
3
3
5
0H, CH
2
2
2
(
m, 2H, H-5, 5′), 6.14 (m, 2H, H-4, 4′), 6.64 (m, 2H, H-3,3′),
7
.81 (br s, 2H, NH).
Gen er a l P r oced u r e for th e Syn th esis of 5,15-Dih ep tyl-
0-(p yr id -4-yl)-20-[(tr im eth ylsilyl)eth yn yl]-21H,23H-p or -
3
1
s, 2H, NH), 0.95 (t, J ) 8.0, 6H, -CH
3
2
-
p h in e (13) a n d 5,15-Dia lk yl-10-(4-iod op h en yl)-20-(p yr id -
CH
2
CH
2
CH
2
CH
CH
CH
3
), 1.75 (m, 4H, -CH
2
2
2
2
3
4
(
5
-yl)-21H,23H-p or p h in es (14a -e). To a degassed solution
50 mL) of the dipyrrylmethane (1 mmol) in CHCl /EtOH (95:
) were successively added 4-iodobenzaldehyde (1 mmol), TFA
(
m, 4H, -CH
2
2
CH CH CH
2
2
3
2
-
3
CH
2
CH
2
CH
2
3
-
C
6
H
4
6 4
I), 8.13 and 9.03 (AA′XX′, J AX ) 5.9, 4H, -C H
(
1.52 mmol), and 4-pyridinecarboxaldehyde (1 mmol). The
solution was protected from light and stirred under argon at
0 °C for 2.5 h. Then DDQ (340 mg, 1.5 mmol, dissolved in
and 9.45 (2 × d, J ) 4.8, 4H, â-H on porphine), 8.84 and 9.42
(
2 × d, J ) 5.1, 4H, â-H on porphine); UV/vis (CH
2 2
Cl ) 306
2
(3.89), 418 (5.44), 517 (4.09), 552 (3.78), 594 (3.51), 651 (3.61);
minimal amount of THF) was added, and the stirring was
continued for an additional 2 h. The reaction mixture was
filtered through an alumina and silica gel pad and washed
+
+
ES -MS (CHCl
for C41 I (729.70): C, 67.49; H, 5.53; N, 9.60. Found: C,
7.41; H, 5.53; N, 9.44.
,15-Dih exyl-10-(4-iod op h en yl)-20-(p yr id -4-yl)-21H ,-
3H-p or p h in e (14d ) was obtained in 5% yield, after purifica-
solution by layered
addition of MeOH, reacting 12d (230 mg, 1 mmol) with
-iodobenzaldehyde32 (232 mg, 1 mmol) and 4-pyridinecarbal-
dehyde (96 µL, 1 mmol), according to the general procedure:
3
/MeOH) m/z 730.80 ([M + H] ). Anal. Calcd
40 5
H N
6
with CHCl
removed under reduced pressure, and the crude product was
purified by FC (CH Cl then CH Cl /EtOAc 95:5 or CH Cl
EtOH 97:3). The first fraction was the 5,15-dialkyl-10,20-bis-
3
until the filtrate was colorless. The solvent was
5
2
2
2
2
2
2
2
tion by two recrystallizations from a CHCl
3
/
(4-iodophenyl)-21H,23H-porphine, the second the desired por-
4
phyrin (14a -e), and the third the 5,15-dialkyl-10,20-bis(pyrid-
-yl)-21H,23H-porphine. Further purification was achieved by
a second FC (CH Cl ) or by repeated recrystallizations from a
solution of CHCl by layered addition of methanol. At the end,
4
1
H NMR (360.14 MHz, CDCl
J ) 7.3, 6H, -CH ), 1.36 (m, 4H, -CH
CH CH CH CH CH
CH ), 2.49 (m, 4H, -CH
), 4.94 (t, J ) 8.0, 4H, -CH
3
) δ -2.75 (br s, 2H, NH), 0.91 (t,
CH CH CH CH CH ),
), 1.78 (m, 4H, -CH
2
2
3
2
2
2
2
2
3
3
1
CH
CH
.49 (m, 4H, -CH
2
2
2
2
2
3
2
-
-
the dark violet solid obtained was washed with hexane and
methanol and dried.
2
CH
2
CH
2
CH
2
3
2
CH
2
CH
2
CH
2
CH
2
3
2
CH
2
CH
2
CH CH
2
2
3
CH ), 7.92
5
,15-Dih ep t yl-10-(p yr id -4-yl)-20-[(t r im et h ylsilyl)et h -
and 8.09 (AA′XX′, J AX ) 8.1, 4H, -C
6
H
4
I), 8.14 and 9.03
yn yl]-21H,23H-p or p h in e(13) was obtained in 12% yield by
reacting meso-heptyl-2,2′-dipyrrylmethane (12e) (244 mg, 1
1
4)
1
8
mmol) with trimethylsilylpropynal (126 mg, 1 mmol) and
-pyridinecarboxaldehyde (96 µL, 1 mmol) in the presence of
(32) Paciorek, K. J . L.; Masuda, S. R.; Shih, J . G.; Nakahara, J . H.
J . Fluorine Chem. 1991, 53, 233-248.
4

4
986 J . Org. Chem., Vol. 66, No. 15, 2001
Rucareanu et al.
+
(
4
AA′XX′, J AX ) 5.9, 4H, -C
6
H
4
N), 8.79 and 9.45 (2 × d, J )
.8, 4H, â-H on porphine), 8.84 and 9.43 (2 × d, J ) 4.8, 4H,
Cl ) 304 (3.93), 418 (5.32), 516
3.99), 552 (3.73), 594 (3.49), 651 3.56); ES -MS (CHCl
676 (4.70); ES -MS (THF/HCOOH) m/z 632.77 ([M + 3H]3+),
2
+
135 15
948.77 ([M + 2H] ) (calcd average mass for C129H N
â-H on porphine); UV/vis (CH
2
2
1895.58).
+
(
3
/MeOH)
I (757.75): C,
8.16; H, 5.85; N, 9.24. Found: C, 68.03; H, 5.98; N, 9.13.
,15-Dih ep t yl-10-(4-iod op h en yl)-20-(p yr id -4-yl)-21H ,-
3H-p or p h in e (14e) was obained in 3% yield, after purifica-
solution by layered
addition of MeOH, reacting 12e (244 mg, 1 mmol) with
5,5′,5′′-[1,3,5-B e n ze n e t r iy lt r is (2,1-e t h y n e d iy l-4,1-
p h en ylen e)]tr is[10,20-d ip r op yl-15-(p yr id -4-yl)-21H,23H-
p or p h in e] (19a ). Air was removed from a solution of 14a (33.7
mg, 50 µmol) and 1,3,5-triethynylbenzene8 (16) (1.87 mg,
+
m/z 758.79 ([M + H] ). Anal. Calcd for C43
6
44 5
H N
,21
5
1
1
2
2.44 µmol) in 10 mL of DMF/Et
h. Then, Pd dba (2.54 mg, 2.78 µmol) and AsPh
2.4 µmol) were added, and deaeration was continued 10 min,
3
N (5:1) by blowing argon for
2
(6.86 mg,
tion by two recrystallizations from a CHCl
3
2
3
3
3
2
before the solution was heated at 35 °C for 5 h. Then, the same
amounts of catalyst were added again, and stirring was
continued for an additional 2 h. The solvent was removed
under reduced pressure, and the crude product was purified
4
-iodobenzaldehyde (232 mg, 1 mmol) and 4-pyridinecarbal-
dehyde (96 µL, 1 mmol), according to the general procedure:
1
H NMR (360.14 MHz, CDCl
J ) 7.3, 6H, -CH ),1.31 (m, 8H, -CH
CH ), 1.49 (m, 4H, -CH CH CH CH CH
CH CH CH CH CH CH ), 2.48 (m, 4H, -CH
CH CH ), 4.92 (t, J ) 7.7, 4H, -CH CH CH
), 7.90 and 8.08 (AA′XX′, J AX ) 8.4, 4H, -C
3
) δ -2.76 (br s, 2H, NH), 0.89 (t,
CH CH CH CH CH
CH CH ), 1.75 (m,
3
2
2
2
2
2
2
-
by FC (CH
porphyrin 14a (13.6 mg, 40%) and 2.2 mg (10%) of the expected
trimer 19a : 1H NMR (360.14 MHz, CDCl
) δ -2.71 (br s, 6H,
NH), 1.33 (t, J ) 7.3, 18H, -CH ), 2.57 (m, 12H, -CH CH
CH ), 4.98 (t, J ) 7.7, 12H, -CH CH CH ), 8.06 and 8.28
AA′XX′, J AX ) 8.1, 12H, -C -), 8.11 (s, 3H, benzenetriyl),
.15 and 8.98 (AA′XX′, J AX ) 5.1, 12H, -C N), 8.81 and 9.49
2 2
Cl ) to yield 13.6 mg (40%) of the unreacted
3
2
2
2
2
2
2
3
4
CH
CH
H, -CH
2
2
2
2
2
2
3
2
2
6
CH
CH
H I),
4
2
-
-
3
2
CH
CH
2
CH
CH
2
3
2
3
2
2
2
3
2
2
-
2
2
3
2
2
3
8
.12 and 9.02 (AA′XX′, J AX ) 5.5, 4H, -C
2 × d, J ) 4.8, 4H, â-H on porphine), 8.83 and 9.41 (2 × d, J
4.8, 4H, â-H on porphine); UV/vis (CH Cl ) 302 (4.06), 418
5.41), 517 (4.09), 552 (3.83), 594 (3.59), 651 (3.66); ES -MS
6 4
H N), 8.78 and 9.43
(
6 4
H
(
8
6 4
H
)
(
(
2
2
+
(2 × d, J ) 4.8, 12H, â-H on porphine), 8.95 and 9.50 (2 × d,
J ) 4.8, 12H, â-H on porphine); UV/vis (CH Cl ) 296 (4.93),
22 (5.91), 516 (4.66), 552 (4.45), 593 (4.20), 651 (4.28); ES -
+
2+
2
2
CHCl
3
/HCOOH) m/z 786.77 ([M + H] ), 393.89 ([M + 2H] ).
I (785.81): C, 68.78; H, 6.16; N, 8.91.
Found: C, 68.65; H, 6.03; N, 9.07.
,15-Dip h en yl-10-(4-iod op h en yl)-20-(p yr id -4-yl)-21H,-
3H-p or p h in e (14f). To a degassed solution of meso-phenyl-
+
4
Anal. Calcd for C45
48 5
H N
3
+
MS (THF/HCOOH) m/z 596.77 ([M + 3H] ), 894.58 ([M +
2
+
2
H] ) (calcd average mass for C123
,5′,5′′-[1,3,5-Ben zen etr iyltr is(2,1-eth yn ed iyl-4,1-p h en -
ylen e)]tr is[10,20-dibu tyl-15-(pyr id-4-yl)-21H,23H-por ph in e]
19b). Reaction, as described for 19a , of 14b (35.1 mg, 50 µmol)
with 16 (1.85 mg, 12.35 µmol) in the presence of Pd dba (2.54
mg, 2.78 µmol) and AsPh (6.81 mg, 22.24 µmol) for 4 h, and
additional 15 h, with subsequent purification by FC (CH Cl ),
afforded 18.1 mg (52%) of the unreacted porphyrin 14b and
.0 mg (9%) of the expected trimer 19b: 1H NMR (360.14 MHz,
CDCl ) δ -2.69 (br s, 6H, NH), 1.28 (t, J ) 7.3, 18H, -CH ),
.81 (m, 12H, -CH CH CH CH ), 2.52 (m, 12H, -CH CH
CH CH ), 4.99 (t, J ) 7.7, 12H, -CH CH CH CH ), 8.06 and
.28 (AA′XX′, J AX ) 8.1, 12H, -C -), 8.11 (s, 3H, benzen-
etriyl), 8.16 and 9.04 (AA′XX′, J AX ) 5.9, 12H, -C N), 8.82
99
H N15 1787.24).
5
5
2
2
1
1
2 2
,2′-dipyrrylmethane (12f) (111 mg, 0.5 mmol) in CH Cl /
(
EtOH 95:5 (50 mL) were successively added 4-iodobenz-
2
3
3
2
aldehyde (116 mg, 0.5 mmol), TFA (1.27 mmol), and 4-py-
ridinecarboxaldehyde (48 µL, 0.5 mmol). The solution was
protected from light and stirred under argon at 20 °C for 24
h. Then DDQ (170 mg, 0.75 mmol, dissolved in minimal
amount of THF) was added, and the stirring was continued
for additional 2 h. The reaction mixture was filtered through
an alumina and silica gel pad and washed with CHCl until
3
the filtrate was colorless. The solvent was removed under
reduced pressure, and the crude product was purified by FC
3
2
2
2
3
3
1
2
2
2
3
2
2
-
2
3
2
2
2
3
8
6 4
H
6
H
4
(
2 2 2 2
CH Cl , then CH Cl /EtOAc 1/1, then EtOAc). The first
and 9.48 (2 × d, J ) 4.8, 12H, â-H on porphine), 8.95 and 9.49
fraction was 5,15-diphenyl-10,20-bis(4-iodophenyl)-21H,23H-
porphine, the second the desired porphyrin 14f, and the third
5
ids obtained were washed with methanol and hexane and
dried. Porphyrin 14f was obtained in 6% yield: H NMR
(
2 × d, J ) 4.8, 12H, â-H on porphine); UV/vis (CH
2 2
Cl ) 297
(
4.86), 423 (5.95), 517 (4.57), 553 (4.30), 595 (3.77), 652 (4.05);
,15-diphenyl-10,20-bis(pyrid-4-yl)-21H,23H-porphine. The sol-
+
3+
ES -MS (THF/HCOOH) m/z 624.80 ([M + 3H] ), 936.73 ([M
2+
+
2H] ) (calcd average mass for C129
,5′,5′′-[1,3,5-Ben zen etr iyltr is(2,1-eth yn ed iyl-4,1-p h en -
ylene)]tris[10,20-dipentyl-15-(pyrid-4-yl)-21H,23H-porphine]
19c). Air was removed from a solution of 14c (36.5 mg, 50
111
H N15 1871.40).
1
5
(
360.14 MHz, CDCl
H, m-, p-phenyl), 8.19-8.21 (m, 4H, o-phenyl), 7.94 and 8.09
AA′XX′, J AX ) 8.1, 4H, -C -I), 8.16 and 9.02 (AA′XX′, J AX
5.9, 4H, -C
N), 8.79 and 8.89 (2 × d, J ) 4.8, 4H, â-H on
porphine), 8.84 and 8.87 (2 × d, J ) 4.8, 4H, â-H on porphine);
UV-vis (CH Cl ) 417 (5.49), 514 (4.09), 549 (3.69), 589 (3.56),
44 (3.39); ES -MS (CHCl
Anal. Calcd for C43 I (741.63): C, 69.64; H, 3.80; N, 9.44.
Found: C, 69.33; H, 3.97; N, 9.46.
,5′,5′′-[1,3,5-Ben zen etr iyltr is(2,1-eth yn ed iyl)]tr is[10,-
0-d ih ep tyl-15-(p yr id -4-yl)-21H,23H-p or p h in e] (18). The
protected porphyrin 13 (5 mg, 7.35 µmol), 1,3,5-triiodoben-
3
) δ -2.84 (br s, 2H, NH), 7.73-7.79 (m,
6
(
)
(
6
H
4
8,21
µmol) and 1,3,5-triethynylbenzene
µmol) in 10 mL of DMF/Et N (5:1) by blowing argon for 1 h.
Then, Pd dba (6.90 mg, 22.54
(16) (1.88 mg, 12.52
6 4
H
3
2
3
(2.58 mg, 2.82 µmol) and AsPh
3
2
2
+
µmol) were added, and deaeration was continued 10 min before
+
6
3
/MeOH) m/z 742.61 ([M + H] ).
the mixture was heated at 35 °C for 4 h. The solvent was
28 5
H N
removed under reduced pressure, and the crude product was
purified by FC (CH
1
2
Cl
2
), to yield 12.2 mg (50%) of 19c:
H
5
NMR (360.14 MHz, CDCl ) δ -2.71 (br s, 6H, NH), 0.96 (t, J
3
2
) 7.3, 18H, -CH ), 1.52 (m, 12H, -CH CH CH CH CH ), 1.76
3
2
2
2
2
3
(m, 12H, -CH CH CH CH CH ), 2.51 (m, 12H, -CH CH CH -
2
2
2
2
3
2
2
2
1
9
zene (15) (0.866 mg, 1.9 µmol), and K
were dissolved in THF (3 mL). The solution was degassed by
bubbling argon for 30 min, and then piperidine (0.2 mL),
2
CO
3
(2.3 mg, 16.8 µmol)
CH CH ), 4.93 (t, J ) 7.3, 12H, -CH CH CH CH CH ), 8.05
2
3
2
2
2
2
3
and 8.26 (AA′XX′, J
AX
) 8.4, 12H, -C H -), 8.13 and 9.02
6
4
(AA′XX′, J AX ) 5.8, 12H, -C H N), 8.11 (s, 3H, benzenetriyl),
6
4
methanol (0.2 mL), and Pd(PPh
3
)
4
(1 mg) were added. The
8.79 and 9.44 (2 × d, J ) 4.8, 12H, â-H on porphine), 8.93 and
9.45 (2 × d, J ) 4.8, 12H, â-H on porphine); UV/vis (CH Cl
297 (4.89), 423 (5.93), 517 (4.64), 553 (4.43), 595 (4.12), 652
mixture was flushed with argon for an additional 10 min and
then heated at 70 °C for 23 h. The solvents were removed
under reduced pressure, and the crude product was purified
by FC (CH
3
2
2
)
+
3+
(4.25); ES -MS (THF/HCOOH) m/z 652.87 ([M + 3H] ), 978.76
([M + 2H]2 ). Anal. Calcd for C135
+
2
Cl
2
/Et
3
N 97:3, then CHCl
3
, then CHCl
3
/EtOH 97:
123
H N15 (1955.55): C, 82.92;
1
) to yield 2.50 mg (72%) of 18: H NMR (360.14 MHz, CDCl
3
)
H, 6.34; N, 10.74. Found: C, 82.44; H, 6.52; N, 10.43
5,5′,5′′-[1,3,5-Ben zen etr iyltr is(2,1-eth yn ed iyl-4,1-p h en -
ylene)]tris[10,20-dihexyl-15-(pyrid-4-yl)-21H,23H-porphine]
(19d ). Reaction of 14d (37.9 mg, 50 µmol) with 16 (1.85 mg,
δ -3.29 (br s, 6H, NH), 0.90 (t, J ) 6.8, 18H, -CH
CH CH CH CH CH CH
CH CH CH ), 1.66 (m, 12H, -CH
), 2.28 (m, 12H, -CH CH CH CH CH
CH CH CH CH CH CH
N), 8.96 (s, 3H,
3
), 1.33 (m,
2
CH
CH
4H, -CH
2
2
2
2
2
2
3
), 1.45 (m, 12H, -CH
2
CH
CH
2
-
-
2
CH
2
2
2
3
2
CH
2
CH
2
CH
2
2
2
CH
3
2
2
2
2
2
CH
2
CH
3
), 4.11
12.32 µmol), as described for 19c, afforded 12.6 mg (50%) of
1
(
(
t, J ) 7.7, 12H, -CH
2
2
2
2
2
2
3
), 8.05 and 8.99
19d : H NMR (360.14 MHz, CDCl
3
) δ -2.70 (br s, 6H, NH),
), 1.37 (m, 12H, -CH CH CH
), 1.49 (m, 12H, -CH CH CH CH CH CH ), 1.78
(m, 12H, -CH CH CH CH CH CH ), 2.51 (m, 12H, -CH
CH CH CH CH ), 4.95 (t, J ) 7.7, 12H, -CH CH CH CH
AA′XX′, 2 × d, J AX ) 5.0, 12H, -C
6
H
4
0.92 (t, J ) 7.3, 18H, -CH
3
2
2
2
-
benzenetriyl), 8.53 and 9.07 (2 × d, J ) 5.0, 12H, â-H on
CH CH CH
2
2
3
2
2
2
2
2
3
porphine), 8.93 and 9.85 (2 × d, J ) 4.5, 12H, â-H on porphine);
2
2
2
2
2
3
2
CH
CH
2
-
2
UV/vis (CH
2
Cl
2
) 301 (4.63), 440 (5.78), 534 (4.39), 581 (4.91),
2
2
2
3
2
2
2
2

Supramolecular Assemblies
J . Org. Chem., Vol. 66, No. 15, 2001 4987
-
CH
3
), 8.05 and 8.27 (AA′XX′, J AX ) 8.4, 12H, -C
6
H
4
-), 8.14
phenyl m- and p-H), 8.08 and 8.30 (AA′XX′, J AX ) 8.2 Hz, 12
H, phenylene H), 8.18 and 9.04 (AA′XX′, J AX)5.9 Hz, 12 H,
pyridine H), 8.20-8.24 (m, 12 H, phenyl o-H), 8.81 and 8.91
(2 × d, J ) 4.5 Hz, 12 H, â-H on porphine outside), 8.93 (s, 12
and 9.03 (AA′XX′, J AX ) 6.2, 12H, -C
6
H
4
N), 8.11 (s, 3H,
benzenetriyl), 8.80 and 9.45 (2 × d, J ) 4.8, 12H, â-H on
porphine), 8.93 and 9.46 (2 × d, J ) 4.8, 12H, â-H on porphine);
UV/vis (CH
2
Cl
2
) 297 (4.80), 423 (5.91), 517 (4.55), 553 (4.31),
2 2
H, â-H on porphine inside); UV/vis (CH Cl ) 352 (4.69), 420
+
+
5
95 (3.87), 652 (4.11); ES MS (THF/HCOOH) m/z 680.93 ([M
(5.85), 515 (4.49), 551 (4.15), 590 (3.81), 646 (3.67); ES -MS
3
+
2+
2+
3+
+
141
3H] ), 1020.90 ([M + 2H] ) (calcd average mass for
15 2039.72).
,5′,5′′-[1,3,5-Ben zen etr iyltr is(2,1-eth yn ed iyl-4,1-p h en -
ylene)]tris[10,20-diheptyl-15-(pyrid-4-yl)-21H,23H-porphine]
19e). Reaction of 14e (39.3 mg, 50 µmol) with 16 (1.88 mg,
(THF/HCOOH) m/z 1140.8 ([M + 2H] ), 760.9 ([M + 3H]
)
C
H
135
N
(calcd average mass for C156 2279.95).
111 3
H N15Si
5
5,5′,5′′-[(2,4,6-Tr iet h yn yl-1,3,5-b en zen et r iyl)t r is(2,1-
eth yn ed iyl-4,1-p h en ylen e)]tr is[10,20-d ip h en yl-15-(p yr id -
4-yl)-21H,23H-p or p h in e] (22b). To a solution of 22a (4.2 mg,
1.84 µmol) in THF (4.8 mL) was added aqueous NaOH (1 M,
2.4 mL), and the mixture was stirred vigorously at 20 °C for
(
1
1
0
CH
CH
2.54 µmol), as described for 19c, afforded 13.5 mg (51%) of
1
9e: H NMR (360.14 MHz, CDCl
.89 (t, J ) 7.3, 18H, -CH ), 1.33 (m, 24H, -CH
), 1.51 (m, 12H, -CH CH CH CH
), 1.79 (m, 12H, -CH CH CH CH CH CH CH
CH CH CH CH CH -CH ), 4.97 (t, J ) 7.7, 12H,
CH CH CH CH CH ), 8.06 and 8.28 (AA′XX′, J AX
.1, 12H, -C -), 8.15 and 9.03 (AA′XX′, J AX ) 5.5, 12H,
N), 8.11 (s, 3H, benzenetriyl), 8.81 and 9.47 (2 × d, J )
.8, 12H, â-H on porphine), 8.95 and 9.48 (2 × d, J ) 4.8, 12H,
â-H on porphine); UV/vis (CH Cl ) 296 (4.92), 423 (5.96), 517
4.64), 553 (4.42), 595 (4.05), 652 (4.22); ES -MS (THF/
3
) δ -2.70 (br s, 6H, NH),
3
2
CH
CH
2
CH
CH
2
-
-
4 h. After evaporation of the THF, CH
organic layer was separated, washed with water, and dried
(MgSO ). The residue obtained after removal of the solvent
was washed thoroughly with MeOH and then with pentane,
yielding 2.8 mg (73%) of 22b: 1H NMR (360.14 MHz, CDCl
)
3
2 2
Cl was added. The
2
3
CH
2
CH
2
CH
3
2
2
2
2
2
2
2
2
2
2
2
2
3
), 2.52 (m,
4
1
2H, -CH
2
2
2
2
2
2
3
-CH CH
2
2
2
2
2
2
3
)
8
-
4
6
H
4
δ -2.79 (s, 6 H, NH), 4.09 (s, 3 H, CtCH), 7.74-7.83 (m, 18
H, phenyl m- and p-H), 8.12 and 8.30 (AA′XX′, J AX ) 8.2 Hz,
12 H, phenylene H), 8.18 and 9.03 (AA′XX′, J AX ) 5.0 Hz, 12
H, pyridine H), 8.20-8.24 (m, 12 H, phenyl o-H), 8.81 and 8.91
(2 × d, J ) 4.6 Hz, 12 H, â-H on porphine outside), 8.92 (s, 12
6 4
C H
2
2
+
(
3
+
2+
HCOOH) m/z 708.99 ([M + 3H] ), 1062.94 ([M + 2H] ) (calcd
average mass for C147 15 2123.88).
,5′,5′′-[1,3,5-Ben zen etr iyltr is(2,1-eth yn ed iyl-4,1-p h en -
ylene)]tris[10,20-diphenyl-15-(pyrid-4-yl)-21H,23H-porphine]
19f). Reaction of 14f (29.3 mg, 39.5 µmol) with 16 (1.48 mg,
.87 µmol) in the presence of Pd dba (1.98 mg, 2.16 µmol) and
AsPh (5.3 mg, 17.3 µmol), as described for 19c, afforded 8.8
mg (46%) of 19f: H NMR (360.14 MHz, CDCl
H, NH), 7.75-7.83 (m, 18H, m-, p-C ), 8.21-8.24 (m, 12H;
o-C ), 8.02 and 8.28 (AA′XX′, J AX ) 8.5, 12H, -C -), 8.17
and 9.02 (AA′XX′, J AX ) 5.9, 12H, -C N), 8.04 (s, 3H,
2 2
H, â-H on porphine inside); UV/vis (CH Cl ) 349 (5.00), 420
H
147
N
(5.90), 515 (4.75), 551 (4.55), 590 (4.38), 646 (4.28); MALDI-
+
5
MS (dithranol) m/z 2063.3 (M ) (calcd average mass for
C
147
H
87
N
15 2063.40).
(
9
5,5′,5′′,5′′′,5′′′′,5′′′′′-[1,2,3,4,5,6-Ben zen eh exa ylh exa k is-
2
3
(2,1-eth yn ed iyl-4,1-p h en ylen e)]h exa k is[10,20-d ip h en yl-
15-(p yr id -4-yl)]-21H,23H-p or p h in e (23). Air was removed
from a solution of 14f (10.1 mg, 13.6 µmol) and 22b (2.8 mg,
3
1
3
) δ -2.79 (br s,
6
6
H
5
1.36 µmol) in 7.7 mL of DMF/Et
3
N (5:1) by blowing argon for
(0.37 mg, 0.40 µmol) and AsPh (1.0
6
H
5
6
H
4
45 min. Then, Pd dba
2
3
3
6
H
4
mg, 3.26 µmol) were added, and deaeration was continued for
10 min, before the mixture was heated at 40 °C for 5 h. Then,
benzenetriyl), 8.80 and 8.90 (2 × d, J ) 4.8, 12H, â-H on
porphine), 8.92 (apparent s, 12H, â-H on porphine); UV/vis
2 3 3
the same amounts of Pd dba and AsPh were added again,
and stirring was continued for 2 h. The solvent was removed
under reduced pressure, and the crude product was purified
(CH
2
Cl
2
) 286 (5.03), 419 (5.99), 515 (4.68), 550 (4.41), 589
+
(4.22), 646 (4.11); ES -MS (THF/HCOOH) m/z 664.77 ([M +
3
+
2+
3
1
4
H] ), 996.62 ([M + 2H] ) (calcd average mass for C141
991.34). Anal. Calcd for C141 15 (1991.34): C, 85.05; H,
.40; N, 10.55. Found: C, 80.13; H, 4.79; N, 9.97.
,5′,5′′-[1,3,5-Ben zen etr iyltr is(2,1-eth yn ed iyl-4,1-p h en -
H
87
N
15
by two successive FC (CHCl
97:3), to yield 0.74 mg (14%) of 23: H NMR (360.14 MHz,
CDCl ) δ -2.92 (s, 12 H, NH), 7.41 (m, 24 H, 10,20-phenyl
3
/MeOH: gradient from 100:0 to
1
87
H N
3
5
m-H), 7.48 (m, 12 H, 10,20-phenyl p-H), 7.91 (m, 24 H, 10,-
20-phenyl o-H), 8.08 and 8.97 (AA′XX′, J AX ) 4.5 Hz, 24 H,
pyridine H), 8.40 and 8.45 (AA′XX′, J AX ) 8.2 Hz, 24 H,
5-phenylene H), 8.68 (d, J ) 4.9 Hz, 12 H, H-2 and H-8), 8.70
(d, J ) 4.9 Hz, 12 H, H-12 and H-18), 8.74 (d, J ) 4.9 Hz, 12
H, H-13 and H-17), 8.92 (d, J ) 4.9 Hz, 12 H, H-3 and H-7);
ylene-2,1-ethynediyl-4,1-phenylene-2,1-ethynediyl-1,4-phen-
ylene)]tris[10,20-diphenyl-15-(pyrid-4-yl)-21H,23H-porphine]
8
(
20). Reaction of 14c (14.3 mg, 19.6 µmol) with 17 (3.7 mg,
4
.9 µmol) in the presence of Pd
AsPh (2.7 mg, 8.82 µmol), as described for 19c, afforded 5.2
mg (42%) of 20: H NMR (360.14 MHz, CDCl
H, NH), 0.96 (t, J ) 7.3, 18H, -CH ), 1.50-1.55 (m, 12H,
CH CH CH CH CH ), 1.77 (m, 12H, -CH CH CH CH CH ),
.52 (m, 12H, -CH CH CH CH CH ), 4.97 (t, J ) 7.0, 12H,
CH CH CH CH CH ), 7.58 and 7.60 (AA′BB′, J AB ) 8.6,
2H), 7.64 and 7.71 (AA′XX′, J AX ) 8.3, 12H), 7.72 (s, 3H,
benzenetriyl) 7.96 and 8.21 (AA′XX′, J AX ) 8.0, 12H) 8.15 and
.03 (AA′XX′, J AX ) 5.8, 12H, -C
N), 8.81 and 9.45 (2 × d,
2 3
dba (1.0 mg, 1.1 µmol) and
3
1
3
) δ -2.71 (br s,
2 2
UV/vis (CH Cl ) 420 (6.08), 515 (4.85), 551 (4.58), 590 (4.49),
+
3+
6
-
2
-
1
3
646 (4.23); ES -MS (THF/HCOOH) m/z 1302.5 ([M + 3H] ),
4
+
2
2
2
2
3
2
2
2
2
3
168 30
977.1 ([M + 4H] ) (calcd average mass for C276H N
2
2
2
2
3
3904.56).
2
2
2
2
3
Com p lex betw een Host Ma cr ocycle 1d a n d Gu est
1
Tr im er 19e. The complex formation was monitored by
NMR spectroscopy. To a CDCl solution of host macrocycle 1d
was added gradually 1 equiv of guest trimer 19e (in concen-
trated CDCl solution), a proton spectrum being registered
H
3
9
6 4
H
J ) 4.8, 12H, â-H on porphine), 8.89 and 9.47 (2 × d, J ) 4.8,
3
1
5
2H, â-H on porphine); UV/vis (CH
17 (4.56), 553 (4.34), 595 (3.93), 651 (4.13); ES -MS (THF/
2
Cl
2
) 361 (5.25), 421 (5.94),
each time. The integration indicates that a new species was
formed with a 1:1 ratio between guest and host. The chemical
shifts of the protons corresponding to the guest porphyrin are
upfield shifted due to the ring current of the three zinc
porphyrins of the host macrocycle. 1H NMR (500.13 MHz,
+
3
+
2+
HCOOH) m/z 853.08 ([M + 3H] ), 1278.94 ([M + 2H] ) (calcd
average mass for C183 15 2556.27).
,5′,5′′-[[2,4,6-Tr is[(t r im et h ylsilyl)et h yn yl]-1,3,5-b en -
H
147
N
5
zen et r iyl]t r is(2,1-et h yn ed iyl-4,1-p h en ylen e)]t r is[10,20-
diph en yl-15-(pyr id-4-yl)-21H,23H-por ph in e] (22a). Air was
removed from a solution of 5,15-diphenyl-10-(4-iodophenyl)-
CDCl
ments: δ -3.15 (br s, 6H, NH), 0.88 (m, 18H, -CH
CH CH CH CH CH CH
), 1.47 (s, 54H, t-Bu), 1.61 (m, 12H, -CH
CH ), 1.74 (s, 36H, o-CH
3
) assignments established with COSY and NOE experi-
3
), 1.25 (m,
24H, -CH
2
2
2
2
2
2
3
), 1.38 (m, 12H, -CH
2
CH
2
2
-
-
2
0-(pyrid-4-yl)-21H,23H-porphine (14f) (22.2 mg, 30 µmol) and
CH
CH
2
CH
CH
2
CH
CH
2
2
CH
CH
2
2
CH
CH
3
2
[(2,4,6-triethynyl-1,3,5-benzenetriyl)tri-2,1-ethynediyl]tris(tri-
2
2
3
3
on Ni-porphine)
CH
on Ni-porphine),
on Zn-porphine), 2.92 and 6.35 (2 ×
apparent d, J ) 5.7, 12H, -C N), 4.76 (m, 12H, -CH CH
CH CH CH CH CH ), 7.15 (s, 12H, m-H on Ni-porphine), 7.35
2
2
mehylsilane) (21) (2.19 mg, 5.0 µmol) in 6.5 mL of DMF/Et
5:1) by blowing argon for 30 min. Then, Pd dba (1.37 mg,
.5 µmol) and AsPh (3.7 mg, 12 µmol) were added, and
3
N
1.99 (s, 36H, o-CH
CH CH CH CH CH
2.68 (s, 18H, p-CH
3
3
on Zn-porphine), 2.30 (m, 12H, -CH
2
2
-
(
1
2
3
2
2
2
2
3
), 2.52 (s, 18H, p-CH
3
3
deaeration was continued for 10 min before the mixture was
heated at 40 °C for 6 h. The solvent was removed under
reduced pressure, and the crude product was purified by two
6
H
4
2
2
-
2
2
2
2
3
(s, 12H, m-H on Zn-porphine), 7.40 and 9.04 (2 × d, J ) 4.5,
12H, â-H on trimer porphine), 7.69 (app. s, 6H), 7.75 (app. s,
6H), 7.77 (app. s, 6H), 7.84 and 8.02 (AA′XX′, J AX ) 8.0, 24H,
phenylene on Ni porphine), 7.90 and 8.08 (AA′XX′, J AX ) 8.0,
successive FC (CHCl
yield 4.2 mg (37%) of 22a : H NMR (360.14 MHz, CDCl
2.79 (s, 6 H, NH), 0.51 (s, 27 H, SiMe ), 7.74-7.83 (m, 18 H,
3
/MeOH: gradient from 100:0 to 98:2), to
1
3
) δ
-
3

4
988 J . Org. Chem., Vol. 66, No. 15, 2001
Rucareanu et al.
1
7
2H, phenylene on trimer porphine), 7.96 (s, 3H, benzenetriyl)
.98 and 8.37 (AA′XX′, J AX ) 6.9, 24H, phenylene on Zn
MHz) δ -3.53 (br s, 12H, NH), 1.46 (s, 54H, t-Bu), 1.87 (s,
72H, o-CH on Zn-porphine), 2.63 (s, 36H, p-CH on Zn-
3 3
porphine), 8.56 and 8.66 (2 × d, J ) 4.8, 24H, â-H on Ni
porphine), 8.75 and 9.29 (2 × d, J ) 4.5, 12H, â-H on trimer
porphine), 8.86 and 8.98 (2 × d, J ) 4.5, 24H, â-H on Zn
porphine); MALDI-TOF-MS (dithranol) m/z 7746.7 (complex
porphine), 2.74 and 6.20 (2 × apparent d, J ) 6.3, 24H,
-C H N), 7.20 (s, 24H, m-H on Zn-porphine), 7.21 and 8.25 (2
6
4
× d, J ) 4.5, 24H, â-H on star porphine,), 7.42 (t, J ) 7.3,
24H, m-phenyl, star porphine), 7.52 (t, J ) 7.3, 12H, p-phenyl
on star porphine,), 7.66 (app s, 6H), 7.71 (app s, 12H), 7.73
1
5
d + 19e) (calcd average mass for C531
622.6 (host 1d ), 2123.0 (guest 19e).
447 3 3
H N39Ni Zn 7746.87),
(m, 24H, o,o′-phenyl on star porphine), 7.85 and 8.26 (m, 48H,
Com p lex betw een h ost m a cr ocycle 1d a n d gu est tr i-
m er 18 was obtained as described previously for the complex
on Zn porphine), 8.10 and 8.21 (AA′XX′ J AX ) 8.0, 24H, on
star porphine), 8.48 and 8.62 (2 × d, J ) 4.5, 24H, â-H on star
porphine), 8.77 and 8.87 (2 × d, J ) 4.5, 48H, â-H on Zn
porphine); MALDI-TOF-MS (ET-matrix DCTB) m/z 9547.3
1
1
d
+ 19e: H NMR (500.13 MHz, CDCl
3
) assignments
established with COSY and NOE experiments δ -2.74 (br s,
6
H, NH), 0.74 (m, 18H, -CH
3
), 1.17 (m, 24H, -CH
2
2
2
CH
CH
CH
2
2
2
CH
CH
CH
2
2
2
-
-
-
(
9
complex 1a + 23) (calcd average mass for C660
468 6
H N54Zn
CH
CH
CH
o-CH
CH
2
3
2
CH
), 1.48 (s, 54H, t-Bu), 1.61 (m, 12H, -CH
CH CH ), 1.81 (s, 36H, o-CH
on Zn-porphine), 2.27 (m, 12H, -CH
CH ), 2.55 (s, 18H, p-CH on Ni-porphine), 2.65 (s, 18H,
p-CH
on Zn-porphine), 3.11 and 6.34 (2 × apparent d, J )
N), 4.70 (m, 12H, -CH CH CH CH CH CH
), 7.20 (s, 12H, m-H on Ni-porphine), 7.32 (s, 12H, m-H
2
CH
2
CH
3
), 1.34 (m, 12H, -CH
2
CH
2
CH
2
CH
CH
547.59), 5643.7 (host 1a ), 3905.9 (guest 23).
2
2
3
3
on Ni-porphine) 1.95 (s, 36H,
2
CH CH CH CH -
Ack n ow led gm en t. This work was supported in part
3
2
2
2
2
by the Swiss National Science Foundation (Project No.
2000-056881.99). NMR spectra on a Bruker Avance
DRX 500 instrument were performed by F. Fehr, mass
spectra by F. Nydegger and I. M u¨ ller. Some MALDI
mass spectra were measured by Dr G. Baykut (Bruker,
Bremen). MALDI-TOF mass spectra of complexes 1d
2
3
3
3
5
CH
.0, 12H, -C
6
H
4
2
2
2
2
2
2
-
3
on Zn-porphine), 7.38 and 8.95 (2 × d, J ) 4.5, 12H, â-H on
trimer porphine), 7.70 (app s, 6H), 7.73 (app s, 6H), 7.83 (app
s, 6H), 7.86 and 8.01 (AA′XX′, J AX ) 8.2, 24H, phenylene on
Ni porphine), 7.97 and 8.37 (AA′XX′, J AX ) 8.8, 24H, phenylene
on Zn porphine), 8.60 and 8.72 (2 × d, J ) 4.9, 24H, â-H on Ni
porphine), 8.64 (s, 3H, benzenetriyl), 8.85 and 8.95 (2 × d, J
+
19e, 1d + 18, and 1e + 23 were measured by H.-U.
Hediger (ETH Z u¨ rich).
)
4.5, 24H, â-H on Zn porphine), 9.40 and 9.84 (2 × d, J )
1
Su p p or tin g In for m a tion Ava ila ble: Copies of H NMR
4
.5, 12H, â-H on trimer porphine); MALDI-TOF-MS (dithranol)
m/z 7519.1 (complex 1d + 18) (calcd average mass for
Zn 7518.57), 5622.8 (host 1d ), 1896.2 (guest 18).
Com p lex betw een Host Ma cr ocycle 1a a n d Gu est
Hexa m er 23. To a CDCl solution of macrocycle 1a was added
equiv of star hexamer 23 (CDCl solution): NMR (500.13
13
for all new compounds, C NMR for compound 3, EI-MS, ESI-
MS, MALDI-MS, MALDI-TOF, and UV-vis spectra. This
material is available free of charge via the Internet at
http://pubs.acs.org.
C
513
H
435
N
39Ni
3
3
3
1
3
J O0015523