Porphyrazines and Norphthalocyanines Bearing Nitrogen Donor Pockets: Metal Sensor Properties

Article abstract of DOI:10.1021/jo9802574

The amino-functionalized porphyrazines 1, 2, and 4 and norphthalocyanines 3 and 5, which were prepared via Linstead macrocyclization reactions of dinitrile precusors, were subject to UV-vis titrations in the presence of inorganic ions. These polydentate macrocycles are able to bind metal ions by the peripheral ligating diazacrown or vicinal diamine entities in addition to metal ion binding within the porphyrazine (norphthalocyanine) cavity. Although 1 only weakly bound Ag(I) and Hg(II), 2 to 5 were superior polydentate ligands. Surprisingly, porphyrazine 4 was a superior ligand for binding 4 equiv of Co(II), Cu(II), Zn(II), and Cd(II) than the corresponding tetracrowned porphyrazine 2. Both 2 and 4 were excellent ligands for peripherally complexing 4 equiv of Ag(I) and Hg(II) and only for one metal, Pb(II), was the crowned system 2 superior to 4. The crowned norphthalocyanine 3 was generally inefficient in the peripheral complexation of inorganic cations, whereas 5 was superior for the peripheral binding of Co(II), Cu(II), Zn(II), Cd(II), and Hg(II) (1 equiv). Again, only with Pb(II) was the crowned system 3 a superior ligand to 5. X-ray crystallographic characterization of diazacrown 12a, porphyrazine 1(M = Mg), and the complexes of crown 12b with Cu(BF₄)₂ and with HClO₄ are reported.

Full text of DOI:10.1021/jo9802574

5806
J . Org. Chem. 1998, 63, 5806-5817
P or p h yr a zin es a n d Nor p h th a locya n in es Bea r in g Nitr ogen Don or
P ock ets: Meta l Sen sor P r op er ties
L. Scott Beall,† Neelakandha S. Mani,‡ Andrew J . P. White,† David J . Williams,†
Anthony G. M. Barrett,*,† and Brian M. Hoffman*,§
Department of Chemistry, Imperial College of Science, Technology and Medicine,
London SW7 2AY, England, Department of Chemistry, Colorado State University,
Fort Collins, Colorado 80524, and Department of Chemistry, Northwestern University,
Evanston, Illinois 60208
Received February 11, 1998
The amino-functionalized porphyrazines 1, 2, and 4 and norphthalocyanines 3 and 5, which were
prepared via Linstead macrocyclization reactions of dinitrile precusors, were subject to UV-vis
titrations in the presence of inorganic ions. These polydentate macrocycles are able to bind metal
ions by the peripheral ligating diazacrown or vicinal diamine entities in addition to metal ion binding
within the porphyrazine (norphthalocyanine) cavity. Although 1 only weakly bound Ag(I) and Hg-
(II), 2 to 5 were superior polydentate ligands. Surprisingly, porphyrazine 4 was a superior ligand
for binding 4 equiv of Co(II), Cu(II), Zn(II), and Cd(II) than the corresponding tetracrowned
porphyrazine 2. Both 2 and 4 were excellent ligands for peripherally complexing 4 equiv of Ag(I)
and Hg(II) and only for one metal, Pb(II), was the crowned system 2 superior to 4. The crowned
norphthalocyanine 3 was generally inefficient in the peripheral complexation of inorganic cations,
whereas 5 was superior for the peripheral binding of Co(II), Cu(II), Zn(II), Cd(II), and Hg(II) (1
equiv). Again, only with Pb(II) was the crowned system 3 a superior ligand to 5. X-ray
crystallographic characterization of diazacrown 12a , porphyrazine 1 (M ) Mg), and the complexes
of crown 12b with Cu(BF4)2 and with HClO4 are reported.
In tr od u ction
electron-rich porphyrazines show unusual UV-vis spec-
tra, redox chemistry,13 electrochemistry, magnetic prop-
erties, etc. In addition, these porphyrazines exhibit
unusual coordination chemistry through binding of metal
ions both within the macrocyclic cavity and by the
peripheral ligating groups. We have also reported the
preparation and full characterization of solitaire-,14
Gemini,15 and star-porphyrazines,16 from the binding of
one, two, and four metal ions to peripheral ligating
groups. Such binding is apparent by profound changes
in the UV-vis spectrum, since the heteroatoms, in
contrast to heteroatom-functionalized phthalocyanines,
are in direct electronic contact with the core aromatic
Phthalocyanines and related tetraazamacrocycles have
found wide applications in diverse areas such as biomedi-
cal agents for diagnosis and therapy,1,2 chemical sensors,3
liquid crystals,4,5 nonlinear optics,6 Langmuir-Blodgett
films,7 and ladder polymers8 and are precursors to new
conducting materials. Recently, we reported on the
synthesis and novel physical properties of porphyrazines
(tetraazaporphyrins) with peripheral heteroatom func-
tionalization, including octathiolates,9 octa(dialkyl)-
amines,10 and octaol derivatives.11 These studies have
been extended to related macrocycles with two, four,12
or six peripheral thiols, amines, or alcohols. All these
(12) Forsyth, T. P.; Williams, D. B. G.; Garrido Montalban, A.; Stern,
C. L.; Barrett, A. G. M.; Hoffman, B. M. J . Org. Chem. 1998, 63, 331.
(13) Mani, N. S.; Beall, L. S.; White, A. J . P.; Williams, D. J .; Barrett,
A. G. M.; Hoffman, B. M. J . Chem. Soc., Chem. Commun. 1994, 1943.
Eichhorn, D. M.; Yang, S.; J arrell, W.; Baumann, T.; Beall, L. S.; White,
A. J . P.; Williams, D. J .; Barrett, A. G. M.; Hoffman, B. M. J . Chem.
Soc., Chem. Commun. 1995, 1703. Lange, S. J .; Beall, L. S.; Mani, N.
S.; Williams, D. J .; White, A. J . P.; Barrett, A. G. M.; Hoffman, B. M.
J . Org. Chem. 1997, 62, 9284.
(14) Baumann, T. F.; Sibert, J . W.; Olmstead, M. M.; Barrett, A. G.
M.; Hoffman, B. M. J . Am. Chem. Soc. 1994, 116, 2639. Baumann, T.
F.; Nasir, M. S.; Sibert, J . W.; White, A. J . P.; Olmstead, M. M.;
Williams, D. J .; Barrett, A. G. M.; Hoffman, B. M. J . Am. Chem. Soc.
1996, 118, 10479. Baumann, T. F.; Barrett, A. G. M.; Hoffman, B. M.
Inorg. Chem. 1997, in press.
† Imperial College.
‡ Colorado State University.
§ Northwestern University.
(1) Bonnet, R. Chem. Soc. Rev. 1995, 19.
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Leznoff, C. C., Lever, A. B. P., Eds.; VCH: New York, 1996; Vol. 4; pp
485-507.
(3) Collins, G. E.; Armstrong, N. R.; Pankow, J . W.; Oden, C.; Brina,
R.; Arbour, C.; Dodelet, J .-P. J . Vac. Sci. Technol. A 1993, 11, 1383.
(4) Bryant, G. C.; Cook, M. J .; Ryan, T. G.; Thorne, A. J . J . Chem.
Soc., Chem. Commun. 1995, 467.
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Am. Chem. Soc. 1982, 104, 5245.
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Lo´pez, F.; Zyss, J . J . Phys. Chem. 1994, 98, 8761.
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(Berlin) 1990, 74, 41.
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(9) Vela´zquez, C. S.; Broderick, W. E.; Sabat, M.; Barrett, A. G. M.;
Hoffman, B. M. J . Am. Chem. Soc. 1990, 112, 7408.
(10) Mani, N. S.; Beall, L. S.; Miller, T.; Anderson, O. P.; Hope, H.;
Parkin, S. R.; Williams, D. J .; Barrett, A. G. M.; Hoffman, B. M. J .
Chem. Soc., Chem. Commun. 1994, 2095.
(15) Sibert, J . W.; Baumann, T. F.; Williams, D. J .; White, A. J . P.;
Barrett, A. G. M.; Hoffman, B. M. J . Am. Chem. Soc. 1996, 118, 10487.
(16) Vela´zquez, C. S.; Broderick, W. E.; Fox, G. A.; Andersen, K.;
Anderson, O. P.; Barrett, A. G. M.; Hoffman, B. M. J . Am. Chem. Soc.
1992, 114, 7416. Vela´zquez, C. S.; Baumann, T. F.; Olmstead, M. M.;
Hope, H.; Barrett, A. G. M.; Hoffman, B. M. J . Am. Chem. Soc., 1993,
115, 9997. Andersen, K.; Anderson, M.; Anderson, O. P.; Baum, S.;
Baumann, T. F.; Beall, L. S.; Broderick, W. E.; Cook, A. S.; Eichhorn,
D. M.; Goldberg, D.; Hope, H.; J arrell, W.; Lange, S. J .; McCubbin, Q.
J .; Mani, N. S.; Miller, T.; Garrido Montalban, A.; Rodriguez-Morgade,
M. S.; Lee, S.; Nie, H.; Olmstead, M. M.; Sabat, M.; Sibert, J . W.; Stern,
C.; White, A. J . P.; Williams, D. B. G.; Williams, D. J .; Barrett, A. G.
M.; Hoffman, B. M. J . Heterocycl. Chem. 1998, 35, in press.
(11) Cook, A. S.; Williams, D. B. G.; White, A. J . P.; Williams, D. J .;
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S0022-3263(98)00257-6 CCC: $15.00 © 1998 American Chemical Society
Published on Web 07/31/1998

Porphyrazines and Norphthalocyanines
J . Org. Chem., Vol. 63, No. 17, 1998 5807
Sch em e 1
Sch em e 2
methyl)amino units. Porphyrazines 1 and 2 differed in
π-system. As such, these interactions are relevant for
the sensing of metal ions in solution. Herein, we now
report the synthesis of aza-crowned porphyrazines17,18
and related multidentate porphyrazines and a study of
the selectivity of their interactions with common inor-
ganic cations.
Resu lts a n d Discu ssion
Syn th esis of P or p h yr a zin es. We set out to prepare
five porphyrazine systems endowed with peripheral
amino-ligating functionality 1 to 5. Two of these com-
pounds 1 and 2 contained four diaza-18-crown-6 ring
systems, porphyrazine 3 contained a single crown ether
entity, and macrocycles 4 and 5 were, respectively,
functionalized with eight and two N-methyl-N-(2-pyridyl-
(17) For related thia-oxa-crowned porphyrazine systems, see: Sibert,
J . W.; Lange, S. J .; Stern, C.; Barrett, A. G. M.; Hoffman, B. M. J .
Chem. Soc., Chem. Commun. 1994, 1751. Lange, S. J .; Sibert, J . W.;
Stern, C.; Barrett, A. G. M.; Hoffman, B. M. Tetrahedron 1995, 51,
8175. Sibert, J . W.; Lange, S. J .; Stern, C.; Barrett, A. G. M.; Hoffman,
B. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 2020. Sibert, J . W.; Lange,
S. J .; Hoffman, B. M.; Williams, D. J .; Barrett, A. G. M. Inorg. Chem.
1995, 34, 2300. van Nostrum, C. F.; Benneker, F. B. G.; Brussaard,
H.; Kooijman, H.; Veldman, N.; Spek, A. L.; Schoonman, J .; Feiters,
M. C.; Nolte, R. J . M. Inorg. Chem. 1996, 35, 959-969.
(18) For structurally related crowned phthalocyanines, see: Koba-
yashi, N.; Opallo, M.; Osa, T. Heterocycles 1990, 30, 389. Musluoglu,
E.; Gu¨rek, A.; Ahsen, V.; Gu¨l, A.; Bekaˆroglu, O¨ . Chem. Ber. 1992, 125,
2337. An, H.; Bradshaw, J . S.; Izatt, R. M.; Yan, Z. Chem. Rev. 1994,
94, 939. Gu¨rek, A. G.; Bekaˆroglu, O¨ . Helv. Chim. Acta 1994, 77, 1616.
Musluoglu, E.; Bekaˆroglu, O¨ . J . Chem. Res., Synop. 1994, 420. Koc¸ak,
M.; Gu¨rek, A.; Gu¨l, A.; Bekaˆroglu, O¨ . Chem. Ber. 1994, 127, 355. Koc¸ak,
M.; Cihan, A.; Okur, A. IÅ.; Bekaˆroglu, O¨ . J . Chem. Soc., Chem.
Commun. 1991, 577. Hamuryudan, E.; Bekaˆroglu, O¨ . J . Chem. Res.,
Synop. 1993, 460. Koc¸ak, M.; Okur, A. I.; Bekaˆroglu, O¨ . J . Chem. Soc.,
Dalton Trans. 1994, 323. Koc¸ak, M.; Okur, A. I.; Bekaˆroglu, O¨ . J . Chem.
Soc., Dalton Trans. 1994, 2023 (correction). van Nostrum, C. F.; Picken,
S. J .; Schouten, A.-J .; Nolte, R. J . M. J . Am. Chem. Soc. 1995, 117,
9957. Kobayashi, N.; Ohya, T.; Sato, M.; Nakajima, S. Inorg. Chem.
1993, 32, 1803. Vacus, J .; Memetzidis, G.; Doppelt, P.; Simon, J . J .
Chem. Soc., Chem. Commun. 1994, 697. Kobayashi, N.; Togashi, M.;
Osa, T.; Ishii, K.; Yamauchi, S.; Hiroaki, H. J . Am. Chem. Soc. 1996,
118, 1073. Sarigu¨l, S.; Bekaˆroglu, O¨ . Chem. Ber. 1989, 122, 291.
that 2 contained pendant N-(2-pyridylmethyl)amino units
rather than the noncoordinating benzylamino group. It
is reasonable to expect that these multidentate ligands
should, in addition to metal ion coordination within the
porphyrazine cavity, be able to peripherally bind up to
four (and perhaps more) (1, 2, and 4) or one (3 and 5)
metal ions. The tetracrowned porphyrazines 1 and 2
should be able to bind metal ions either within the crown
ether cavities and/or within the meso-pockets.17
Following the methods of Sheppard19 for the synthesis
of dinitrile 10a , sequential double-reductive alkylation
(19) Begland, R. W.; Hartter, D. R.; J ones, F. N.; Sam, D. J .;
Sheppard, W. A.; Webster, D. W.; Weigert, F. J . J . Org. Chem. 1974,
39, 2341.

5808 J . Org. Chem., Vol. 63, No. 17, 1998
Beall et al.
Sch em e 3
Sch em e 4
of DAMN (6) using 2-pyridinecarboxaldehyde gave 2,3-
bis[(2-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile (10b)
(Scheme 1). Iodide 11, which was readily available from
pentaethylene glycol, was condensed with diamine 10a
using cesium carbonate in DMF20 at 50 °C to provide the
corresponding diazacrown 12a as a mixture of E and Z
isomers (50%). Recrystallization gave the corresponding
pure Z isomer, the structure of which was confirmed by
X-ray crystallography (see below). Attempted formation
of crown ether 12a using the ditosylate corresponding to
11 with potassium tert-butoxide, sodium or potassium
hydrides, or sodium or potassium carbonates as base or
from the reaction of 11 using sodium or potassium
hydrides as base or at higher temperatures gave signifi-
cantly reduced yields of crown 12a (0-15%). Similar to
the synthesis of diazaoxocrown ether 12a , slow addition
of a solution of diamine 10b and diiodide 11 in DMF to
a suspension of cesium carbonate in DMF afforded the
crystalline crown 12b in 55% yield (Scheme 2).
Linstead macrocyclization21 of dinitriles 12a and 12b,
respectively, gave porphyrazine 1 (M ) Mg, 25%) and 2
(M ) Mg, 16%). Demetalation of 1 (M ) Mg) gave
porphyrazine 1 (M ) 2H), and subsequent remetalation
with Ni(OAc)2 gave porphyrazine 1 (M ) Ni) (Scheme 2).
Dinitrile 13, prepared by dimethylating dinitrile 10b
(71%), was template macrocyclized to reveal porphyrazine
4 (13%) (Scheme 3). Mixed Linstead macrocyclization
reactions of dinitriles 1422 with 12a and 14 with 12b
followed by removal of the magnesium ions with trifluo-
roacetic acid were successfully used to prepare the
Sch em e 5
norphthalocyanines 15a (11%) and 15b (9%) (Scheme 4).
Norphthalocyanine 15a when heated in the presence of
MnBr2 preferentially coordinated Mn(II) within the
central cavity, giving metalated norphthalocyanine 3. The
Mn(II) ion readily oxidized within the central cavity and,
during the workup of the reaction, exchanged its bromide
ligand for chloride when treated with brine, to give
exclusively the axial chloride 3. Mixed Linstead macro-
cyclization of dinitrile 13 in the presence of excess
dinitrile 14 gave, after demetalation, norphthalocyanine
5 (M ) 2H) (10%), which was remetalated by reaction
with manganese(II) bromide to produce, on workup,
norphthalocyanine 5 (M ) MnCl) (85%) (Scheme 5).
X-r a y Cr yst a llogr a p h ic St r u ct u r e Det er m in a -
tion s of 12a , 1 (M ) Mg), 12b‚Cu (BF 4)2, a n d 12b‚
(HClO4)2. Recrystallization of the mixture of geometric
isomers of crown 12a from ethyl acetate gave the desired
Z isomer, and its structure was verified by X-ray crystal-
lography (Figure 1). The molecule has crystallographic
C2 symmetry about an axis bisecting both the CdC
double bond and the ethylene spacer unit between the
second and third oxygen atoms of the polyether chain.
This symmetry results in an anti disposition of the two
benzyl groups, each of which has its methylene hydrogen
atoms directed toward polyether oxygen atoms. The
conformation is thus stabilized by a total of four weak
C-H‚‚‚O hydrogen bonds. There are no intermolecular
(20) Vriesema, B. K.; Buter, J .; Kellogg, R. M. J . Org. Chem. 1984,
49, 110. Ostrowicki, A.; Koepp, E.; Vo¨gtle, F. Top. Curr. Chem. 1991,
161, 37.
(21) Linstead, R. P.; Whalley, M. J . Chem. Soc. 1952, 4839.
(22) Tamao, K.; Sumitani, K.; Kumada, M. J . J . Am. Chem. Soc.
1972, 94, 4374. Cuellar, E. A.; Marks, T. J . Inorg. Chem. 1981, 20,
3766.

Porphyrazines and Norphthalocyanines
J . Org. Chem., Vol. 63, No. 17, 1998 5809
F igu r e 1. Solid-state molecular structure of 12a showing also
the intramolecular C-H‚‚‚O stabilizing interactions. The C-H‚
‚‚O hydrogen bonding geometries are as follows: C‚‚‚O and
H‚‚‚O distances (Å) and C-H‚‚‚O angles (deg); (a) 3.39, 2.43,
179; (b) 3.27, 2.34, 161 (the C-H distances have been normal-
ized to 0.96 Å).
F igu r e 3. One of the hydrogen-bonded dimer pairs present
in the crystals of 1 [M ) Mg]. The O‚‚‚O hydrogen bonding
contacts are 2.76 and 2.89 Å (the aqua hydrogen atom positions
could not be determined).
12a ), whereas in rings B and C they are syn. In view of
the high degree of thermal vibration/disorder present
within some of these peripheral macrocycles, we have not
attempted to analyze any of the potential intramolecular
C-H‚‚‚O interactions. The only notable feature of the
packing of the molecules is the formation of hydrogen-
bonded dimer pairs wherein the aqua ligand on one
molecule is directed into the center of the diazaoxomac-
roring B of a centrosymmetrically related counterpart
and vice versa (Figure 3).
Double-armed diazaoxocrown ethers can bind metals
via the macroring alone or in combination with either
one or both of the pendant arms. Assuming both arms
participate, they may be on the same or opposite sides
of the macroring. Upon standing, 12b‚Cu(BF4)2 formed
as a deep blue crystalline solid out of a solution of 12b
and Cu(BF4)2 in methanol. The crystal structure of this
product reveals (Figure 4) that 12b acts as a pentaden-
tate ligand, binding to copper via the two macroring
nitrogen atoms, the two pendant pyridine nitrogen atoms,
and one of the macroring oxygen atoms in a distorted
square-pyramidal geometry (the oxygen atom occupying
the apical position). The four Cu-N distances are in the
range 1.970(5)-2.068(6) Å, those to the macroring nitro-
gen atoms being noticeably longer than those to the
pendant pyridyl nitrogen atoms; the Cu-O distance is
significantly longer at 2.314(5) Å. The Cu(II) ion lies 0.27
Å above the plane of the four donor nitrogen atoms in
the direction of the oxygen atom. There are no intermo-
lecular contacts of note.
In several metalation attempts using transition-metal
perchlorate salts, [Co(ClO4)2‚xH2O, Cr(ClO4)3‚6H2O, Ni-
(ClO4)2‚6H2O, Zn(ClO4)2‚6H2O, and as a control HClO4],
crystal formation occurred without the characteristic
colors of transition metal complexes. These compounds
were revealed to be the perchlorate salt of the diproto-
nated ligand, 12b‚(HClO4)2 (Figure 5). A noticeable
feature of this structure is that the pendant pyridinium
moieties lie on opposite sides of the macroring (cf. the
same side in 12b‚Cu(BF4)2 but similar to that adopted
in the related species 12a ) emphasizing the conforma-
F igu r e 2. Molecular structure of 1 (M ) Mg).
π-π stacking interactions involving the aromatic rings.
All attempts to prepare metal salt complexes [AgBF4,
CdCl2, CoCl2, CaCl2, Zn(BF4)2, KBr, NaBr, Hg(ClO4)2] of
crown 12a , however, failed to provide crystalline materi-
als suitable for X-ray crystallography.
Crystals of 1 (M ) Mg) suitable for X-ray analysis were
grown from ethyl acetate/hexanes. The magnesium atom
is bound, as expected, to the four central porphyrazine
nitrogen atoms in a slightly distorted square pyramidal
geometry, the fifth, apical, coordination site being oc-
cupied by an aqua ligand (Figure 2). The metal atom
lies 0.54 Å out of the basal plane toward the oxygen atom.
The Mg-N distances do not differ significantly and are
in the range 2.008(7)-2.042(7) Å; the Mg-O bond length
is 2.006(7) Å. The porphyrazine core and the eight
azapolyether nitrogen atoms are dished away from the
magnesium center and its coordinated oxygen atom, the
eight outer nitrogen atoms lying, on average, 0.40 Å out
of the plane of the central four coordinated nitrogens. The
benzyl substituents on the four peripheral azapolyether
macrocycles adopt two distinct orientationssin rings A
and D these groups are in an anti disposition (i.e., a
geometry analogous to that observed in the structure of

5810 J . Org. Chem., Vol. 63, No. 17, 1998
Beall et al.
Ta ble 1. Su m m a r y of Ability of P or p h yr a zin e 1 (M )
Ni), 2, a n d 4 To Coor d in a te Meta l Ca tion s on th e
P er ip h er y (Ba sed on Uv-vis Titr a tion s)a
porphyrazine
metal salt
KClO4
Cr(ClO4)3‚6H2O
Mn(ClO4)2‚6H2O
CoCl2
Ni(ClO4)‚6H2O
CuCl2
Zn(ClO4)2‚6H2O
AgBF4
CdCl2
1 (M ) Ni)
2 (M ) Mg)
4
-
-
-
-
-
-
-
-
-
-
very good
-
excellent
-
-
-
very good
good
excellent
excellent
very good
excellent
excellent
-
-
poor
-
excellent
good
excellent
excellent
Hg(ClO4)2‚3H2O
Pb(NO3)2
poor
-
a
Qualitative rankings shown are based on molar equivalents
of metal salt per peripheral chelate necessary to effect no further
change in the UV-vis titration: -, no effect in UV-vis; poor, 25
equiv; good to very good, 10-2 equiv; excellent, 1 equiv.
F igu r e 4. Molecular structure of 12b‚Cu(BF4)2. Selected bond
lengths (Å) and angles (deg): Cu-N(1) 2.068(6), Cu-N(16)
2.046(5), Cu-N(25) 1.970(5), Cu-N(32) 1.994(5), Cu-O(13)
2.314(5); N(1)-Cu-N(16) 84.4(3), N(1)-Cu-N(25) 82.7(2),
N(16)-Cu-N(32) 82.6(2), N(25)-Cu-N(32) 106.1(2), N(1)-
Cu-O(13) 102.4(2), N(16)-Cu-O(13) 78.3(2), N(25)-Cu-
O(13) 115.1(2), N(32)-Cu-O(13) 90.8(2).
F igu r e 5. Solid-state structure of the dication of 12b‚(HClO4)2
showing also the stabilizing intramolecular hydrogen bonding
interactions and the intermolecular N-H‚‚‚O link to one of
the perchlorate anions. The N-H‚‚‚O, C-H‚‚‚N, and C-H‚‚‚
O hydrogen bonding geometries are as follows for the X‚‚‚Y
and H‚‚‚Y distances (Å) and X-H‚‚‚Y angles (deg): (a) 2.78,
1.92, 158; (b) 3.01, 2.26, 135; (c) 3.08, 2.30, 146; (d) 3.09, 2.41,
128 (the N-H and C-H distances have been normalized to
0.90 and 0.96 Å, respectively).
F igu r e 6. Porphyrazine 1 (M ) Ni) titrated with AgBF4 (0,
2, 4, 8, 20, 40, >100 equiv).
tion to the peripheral nitrogen atoms ultimately results
in a spectrum that resembles an unsubstituted porphyra-
zine or phthalocyanine.9,16,17 Binding exactly 4 equiv of
a particular metal, one in each of the crown rings, is the
maximal result for porphyrazine 1 (M ) Ni) unless
additional meso-pocket binding is observed.17 This was
realized with AgBF4 (Figure 6) and Hg(ClO4)2. Unfor-
tunately, to force the total disappearance of the n-π*
peak (at 538 nm) and the sharpening of the Q-band (at
602 nm), greater than 100 equiv of either AgBF4 or Hg-
(ClO4)2 were required, thus demonstrating that por-
phyrazine 1 (M ) Ni) is not an efficient ligand for
peripheral metal-ion binding.
Porphyrazine 1 (M ) Mg), in the solid state, has two
adjacent crown ether rings (A and D in Figure 2) in an
orientation similar to that of the starting dinitrile 12a ;
the benzyl groups are on opposite sides of the crown ether
ring. The other pair of crown ether rings (B and C)
adjusts to place the two benzyl groups on the same side
of the ring, making the ring more accessible for metal
coordination (Figure 2). Evidence suggests that the
conformation in solution might be the same. In both the
tional flexibility of this new ligand system. As in 12a ,
the conformation of the molecule is stabilized via in-
tramolecular hydrogen bonding. Here, this involves the
two benzylic methylene hydrogen atoms of one of the
pendant groups and the pyridinium N-H hydrogen atom
of the other. The pyridinium N-H hydrogen atom of the
former is involved in a cation‚‚‚anion hydrogen bond to
one of the perchlorate oxygen atoms. There are no
intermolecular π-π interactions.
P er ip h er a l Meta l Ion Bin d in g by th e P or p h yr a -
zin es 1, 2, a n d 4 a n d Nor p h th a locya n in es 3 a n d 5.
UV-vis titrations were performed with several metal
salts (see Table 1) to investigate the metal-binding
capabilities of porphyrazine 1 (M ) Ni). In the UV-vis
spectrum of aminoporphyrazines, the disappearance of
the n-π* absorbance and a sharpening of the Q-band
indicates metal coordination to the peripheral nitrogen
atoms. Because the nitrogen n electrons are no longer
available to the porphyrazine π system, metal coordina-

Porphyrazines and Norphthalocyanines
J . Org. Chem., Vol. 63, No. 17, 1998 5811
F igu r e 7. Porphyrazine 2 (M ) Mg) titrated with Hg(ClO4)2‚
3H2O (0, 1, 2, 3, 4, 6 equiv).
F igu r e 8. Norphthalocyanine 3 titrated with Pb(NO3)2‚6H2O
(0, 0.5, 1, 2, 4 equiv).
phyrazine 2 (M ) Mg) was able to coordinate Pb(II) as
effectively as Hg(II) and Ag(I). UV-vis titrations were
consistent with porphyrazine 2 (M ) Mg), also being able
to coordinate Cu(II), Co(II), Zn(II), and Cd(II) although
less effectively than Hg(II), Ag(I), or Pb(II) as 20-40
equiv were needed for the disappearance of the n-π*
peak and the sharpening of the Q-band.
UV-vis titrations of porphyrazine 1 (M ) Ni) there is a
dramatic change when going from 0 to 2 equiv of a metal
salt and comparatively little change until porphyrazine
1 (M ) Ni) is treated with greater than 100 equiv of a
metal salt (Figure 6). Overall, the benzyl groups may
suppress peripheral coordination of metal ions. In
contrast, the corresponding porphyrazine 2 (M ) Mg) has
pendent 2-pyridylmethyl groups, which may themselves
enhance peripheral metal ion binding (they are clearly
double-armed diazacrown entities) by enveloping the
cation in a similar fashion as bicyclic cryptands. Double-
armed diazaoxocrown ethers bind a wide range of both
alkaline earth and transition-metal cations, and a wealth
of examples bearing nitrogens at opposite sides of the
macrocycle have been reported.23 The fusion of a diaza-
crown ether and an ethylenediamine derivative24 in 12b
and ultimately 2 (M ) Mg) ought to offer enhanced metal
ion binding properties. Indeed, as is discussed in the
previous section, the crown 12b forms a square-pyramid
complex with copper(II).
Porphyrazine 2 (M ) Mg) was titrated with KClO4, Cr-
(ClO4)3‚6H2O, Mn(ClO4)2‚6H2O, CoCl2, Ni(ClO4)2‚6H2O,
CuCl2, Zn(ClO4)2‚6H2O, AgBF4, CdCl2, Hg(ClO4)2‚3H2O,
and Pb(NO3)2. With the exchange of benzyl for 2-py-
ridylmethyl, the ability of porphyrazine 2 (M ) Mg) to
coordinate Hg(II) (Figure 7) and Ag(I) improved dramati-
cally. Instead of requiring over 100 equiv of metal salt
to effect the disappearance of the n-π* peak and the
sharpening of the Q-band, the UV-vis spectrum no
longer changed after 6 equiv. Not only does the coordi-
nating ability improve for Hg(II) and Ag(I), but por-
Norphthalocyanine 3, being very soluble in organic
solvents, was subject to UV-vis titrations with Cu(OAc)2
and other metal salts. The n-π* transition of the
electron lone pairs on the two peripheral nitrogen atoms
should disappear if a metal coordinates to these nitrogens
because the electron lone pairs would no longer be
available to the norphthalocyanine ring system. Similar
to porphyrazines 1 and 2, a sharpening of the Q-band
accompanied the disappearance of the n-π* peak ulti-
mately leading to a spectrum that resembled the analo-
gous porphyrazine or phthalocyanine derivative. In
norphthalocyanines, however, the Q-band will sharpen
to resemble a C2v-symmetric phthalocyanine that has a
split Q-band due to the degeneracy of the eg molecular
orbitals. The UV-vis titration with Cu(OAc)2 showed
that norphthalocyanine 3 coordinated Cu(II), but 100
equiv of Cu(II) was needed to effect the complete disap-
pearance of the n-π* peak at 512 nm. UV-vis titrations
of norphthalocyanine 3 and the metal salts of Pb(II), Hg-
(II), Ag(I), Zn(II), Co(II), and Cd(II) all resulted in
disappearance of the n-π* peak at 512 nm. Binding of
exactly one metal on the periphery is the maximal result
for the norphthalocyanines. Of all the metals that
norphthalocyanine 3 coordinated, Pb(II) exhibited the
strongest binding. However, more than 2 equiv of even
this metal was required to effect full coordination (Figure
8). Hg(II) and Ag(I) experienced similar binding to Pb-
(II) and Zn(II), Co(II), and Cd(II) all needed greater than
10 equiv. As in porphyrazine 2 (M ) Mg), the crown ring
may impede coordination of the metal, and to study its
effect the pyridylmethyl-methyl porphyrazine 4 and
norphthalocyanine 5 were examined.
(23) For examples, see: Gandour, R. D.; Fonczek, F. R.; Gatto, V.
J .; Minganti, C.; Schultz, R. A.; White, B. D.; Arnold, K. A.; Mazzocchi,
D.; Miller S. R., Gokel G. W. J . Am. Chem. Soc. 1986, 108, 4078. Gokel
G. W. Chem. Soc. Rev. 1992, 92, 39. Tsukube, H.; Yamashita, K.;
Iwachido, T.; Zenki, M. J . Org. Chem. 1991, 56, 268. Tsukube, H.;
Minatogawa, H.; Munakata, M.; Toda, M.; Matsumoto, K. J . Org.
Chem. 1992, 57, 542.
(24) Bailey, N. A.; McKenzie, E. D.; Worthington, J . M. J . Chem.
Soc., Dalton Trans. 1973, 1227. (b) Li, C.-K.; Tang, W.-T.; Che, C.-M.;
Wong, K.-Y.; Wang, R.-J .; Mak, T. C. W. J . Chem. Soc., Dalton Trans.
1991, 1909.
UV-vis titrations of porphyrazine 4 with KClO4, Cr-
(ClO4)3‚6H2O, Mn(ClO4)2‚6H2O, CoCl2, Ni(ClO4)2‚6H2O,

5812 J . Org. Chem., Vol. 63, No. 17, 1998
Beall et al.
F igu r e 9. Porphyrazine 4 titrated with CoCl2 (0, 1, 2, 3, 4
F igu r e 10. Norphthalocyanine 5 titrated with Cu(OAc)2 (0.0,
equiv).
0.25, 0.50, 1.0 equiv).
CuCl2, Zn(ClO4)2‚6H2O, AgBF4, CdCl2, Hg(ClO4)2‚3H2O,
and Pb(NO3)2 showed that the crown ether rings in
porphyrazine 2 (M ) Mg) were necessary only to bind
Pb(II). Without the crown ether rings of porphyrazine 2
(M ) Mg), porphyrazine 4 readily coordinated the first-
row transition metals Co(II), Cu(II), and Zn(II). Only a
slight excess of the metal salt was required before the
n-π* peak disappeared and the Q-band sharpened [for
example, see Figure 9 for Co(II)]. Porphyrazine 4 also
coordinated Hg(II), Cd(II), and Ag(I). Both porphyrazines
4 and 2 (M ) Mg) fully coordinated Hg(II), and porphyra-
zine 4 coordinated Cd(II) better than porphyrazine 2 (M
) Mg). Porphyrazine 2 (M ) Mg) readily coordinated
Pb(II) but porphyrazine 4 did not, indicating that the
crown ether ring is necessary to bind Pb(II) around the
periphery. Porphyrazine 2 (M ) Mg) fully coordinated
Ag(I) as seen by the disappearance of the n-π* peak and
the sharpening of the Q-band. However, in the visible
spectrum of porphyrazine 4 in the presence of Ag(I), the
n-π* peak disappeared but the Q-band remained broad
and only shifted slightly to a shorter wavelength.
A summary of the metal-binding abilities of porphyra-
zines 1 (M ) Ni), 2 (M ) Mg), and 4 is shown in the Table
1. In general, compared to porphyrazine 1 (M ) Ni),
there is an improvement in metal coordinative ability in
the series porphyrazine 4 > 2 (M ) Mg) > 1 (M ) Ni),
with Pb(II) being the only exception. The crown ether
and 2-pyridylmethyl moieties are necessary to bind Pb-
(II), whereas only the 2-pyridylmethyl moieties are
necessary for the binding of Co(II), Cu(II), Zn(II), Ag(I),
Cd(II), and Hg(II).
ether ring [compare 3 and 5 (M ) MnCl)] dramatically
improved the peripheral metal-binding capabilities. Slow
evaporation of a 1:1 mixture of norphthalocyanine 5 (M
) MnCl) and Cu(OAc)2 or CoCl2 gave the bimetallic
complexes 16a and 16b. Unfortunately, neither of these
substances were obtained suitably crystalline for X-ray
structure determinations. The metal-binding abilities of
norphthalocyanines 3 and 5 (M ) MnCl) are summarized
in Table 2. The results parallel those of porphyrazines
2 (M ) Mg) and 4 in that with the removal of the crown
ring the ability to coordinate Pb(II) is lost; however, in
norphthalocyanine 5 (M ) NiCl) the ability to coordinate
Ag(I) is lost as well.
Since the octakis[N-methyl-N-(2-pyridylmethyl)amino]-
porphyrazine 4 was superior for peripheral metal ion
binding than either of the crowned porphyrazines 1 or
2, the norphthalocyanine system 5 (M ) MnCl) was
investigated. UV-vis titration of 5 (M ) MnCl) with Cu-
(OAc)2 was complete with 1 equiv (Figure 10). Nor-
phthalocyanine 5 (M ) MnCl) also coordinated Cd(II) and
Co(II) as effectively as Cu(II); however, full coordination
of Zn(II) and Hg(II) required 2 equiv of metal salt. Once
again, with the exception of Pb(II), removal of the crown
Con clu sion s
It is clear that the porphyrazines 1, 2, and 4 and the
norphthalocyanines 3 and 5 are able to bind inorganic
metal ions to the peripheral ligating functionality with
significant changes in the UV-vis spectra. In general,
with the exception of the binding of Pb(II), the macro-
cycles functionalized with pendant N-methyl-N-(2-py-
ridylmethyl)amino groups 4 and 5 were superior ligands

Porphyrazines and Norphthalocyanines
J . Org. Chem., Vol. 63, No. 17, 1998 5813
Ta ble 2. Su m m a r y of th e Ability of Nor p h th a locya n in e
3 a n d 5 (M ) Mn Cl) to Coor d in a te Meta l Ca tion s on th e
P er ip h er y (Ba sed on UV-vis Titr a tion s)a
to a rapidly stirring solution of imine 7 (20.0 g, 101.5 mmol)
in MeOH (250 mL) and THF (375 mL). After the addition was
complete, the solution was stirred for 15 min and poured into
rapidly stirring ice-H2O (2.5 L). After 15 min, the solid was
collected via vacuum filtration, washed with H2O (500 mL)
and dried under vacuum to give dinitrile 8 (16.4 g, 81%) as a
dark tan solid: mp 120-123 °C; Rf 0.50 (EtOAc); IR (DRIFTS)
norphthalocyanine
metal salt
NaBr
KBr
CaCl2
3
5 (M ) MnCl)
-
-
-
-
-
-
-
-
1
νmax 3387, 3332, 3215, 2219, 2213, 1612, 1598, 1370 cm-1; H
-
NMR (CDCl3/DMSO-d6, 270 MHz) δ 3.72 (2H, d, J ) 6.4 Hz),
4.79 (2H, s), 4.99 (1H, t, J ) 6.4 Hz), 6.57-6.62 (1H, m), 6.69
(1H, d, J ) 7.7 Hz), 7.06-7.12 (1H, m), 7.90 (1H, d, J ) 4.7
Hz); 13C NMR (DMSO, 75 MHz) δ 51.0, 108.4, 108.9, 116.2,
117.2, 121.7, 122.9, 137.4, 149.7, 159.0 (C(2)Pyr); MS (CI, NH3)
m/z 200 (M + H)+, 107 (M - PyrCH2)+; HRMS (CI, NH3) m/z
calcd for C10H10N5 (M + H)+ 200.0936, found 200.0940. Anal.
Calcd for C10H9N5: C, 60.29; H, 4.55; N, 35.15. Found: C,
60.03; H, 4.26; N, 34.78.
-
BaCl2
-
Cr(ClO4)3‚6H2O
Mn(ClO4)2‚6H2O
Fe(ClO4)3‚xH2O
Co(BF4)2‚6H2O
Ni(ClO4)2‚6H2O
Cu(OAc)2
Zn(ClO4)2‚6H2O
RuCl3‚H2O
AgBF4
-
-
-
poor
-
very poor
poor
-
good
poor
good
good
excellent
-
excellent
very good
-
2-[(2-P yr id ylm et h ylen e)a m in o]-3-[(2-p yr id ylm et h yl)-
a m in o]-2(Z)-bu ten e-1,4-d in itr ile (9). CF3CO2H (5 drops)
was added to dinitrile 8 (15.0 g, 75.4 mmol) and 2-pyridin-
ecarboxaldehyde (12.1 g, 113.1 mmol) in MeOH (150 mL). After
1 h, a precipitate began to form, and after 5 h, the solid was
collected by vacuum filtration and was washed with Et2O (300
mL) to give imine 9 (17.2 g, 79%) as a yellow solid: mp 149-
151 °C; Rf 0.20 (EtOAc); IR (DRIFTS) νmax 3262, 2236, 2203,
-
CdCl2
Hg(ClO4)2‚6H2O
Pb(NO3)2
excellent
very good
-
a
Qualitative rankings shown are based on molar equivalents
of metal salt per peripheral chelate necessary to effect no further
change in the UV-vis titration: -, no effect in UV-vis; poor, 100
equiv; good to very good, 25-4 equiv; excellent, 1 equiv.
1606, 1595, 1563, 1435 cm-1 1H NMR (CDCl3, 270 MHz) δ
;
2.20 (1H, br s), 4.77 (2H, s), 7.28-7.38 (3H, m), 7.71-7.81 (2H,
m), 8.00 (1H, d, J ) 7.9 Hz), 8.50 (1H, s), 8.62 (1H, d, J ) 4.5
Hz), 8.69 (1H, d, J ) 5.0 Hz); 13C NMR (DMSO, 75 MHz) δ
51.1, 102.7, 113.5, 113.9, 122.0, 122.4, 123.3, 125.9, 137.2,
137.6, 149.8, 150.3, 154.1, 155.5, 157.3; MS (CI, NH3) m/z 289
(M + H)+, 198 (M - PyrCH2 + 2H)+; HRMS (CI, NH3) m/z
calcd for C16H13N6 (M + H)+ 289.1202, found 289.1201. Anal.
Calcd for C16H12N6: C, 66.66; H, 4.20; N, 29.15. Found: C,
66.70; H, 4.03; N, 28.92.
for the formation of star and solitaire complexes in
solution than the corresponding crowned25 macrocycles
2 and 3. These results are relevant to the development
of selective ion optical sensors.
Exp er im en ta l Section
Reactions were conducted in oven- or flame-dried glassware
under N2. Reaction temperatures reported refer to external
bath temperatures. Solvents used in chromatography were
BDH AnalR or GPR grade and were used without further
purification. Solvents used for reactions were distilled prior
to use: THF, DME, and Et2O (from sodium-benzophenone
ketyl); CH2Cl2 and MeCN (from CaH2); DMF [predried over
BaO, distilled from neutral alumina (activity I)]; MeOH,
1-propanol, and 1-butanol (from Mg). All other reagents were
purchased from commercial sources and were used without
further purification.
TLC was performed on Merck Kieselgel 60 F-254 glass
plates. Unless stated to the contrary, chromatography was
carried out on Merck Kieselgel 60 (230-400 mesh) (eluants
are given in parentheses). Unless stated to the contrary,
organic extracts were dried over Na2SO4 or MgSO4. All
solvents were evaporated at or below 50 °C under reduced
pressure using a rotary evaporator.
2,3-Bis[(2-p yr id ylm eth yl)a m in o]-2(Z)-bu ten e-1,4-d in i-
tr ile (10b). NaBH4 (2.30 g, 60.1 mmol) was slowly added to
imine 9 (17.3 g, 60.1 mmol) in MeOH (150 mL) and THF (225
mL). After the addition was complete, the solution was stirred
for 15 min and poured into rapidly stirring ice-H2O (2.0 L).
After 15 min, the solid was collected via vacuum filtration,
washed with H2O (500 mL), and dried under vacuum to give
dinitrile 10b (13.5 g, 78%) as a dark tan solid: mp 90-93 °C;
Rf 0.16 (EtOAc); IR (DRIFTS) νmax 3292, 2205, 1605 cm-1; 1H
NMR (CDCl3, 270 MHz) δ 4.43 (4H, d, J ) 5.9 Hz), 4.95-4.98
(2H, m), 7.20-7.27 (4H, m), 7.66-7.72 (2H, m), 8.54 (2H, d, J
) 5.0 Hz); 13C NMR (DMSO, 75 MHz) δ 50.9, 113.4, 114.7,
122.1, 122.8, 137.0, 149.3, 156.6; MS (CI, NH3) m/z 291 (M +
H)+, 198 (M - PyrCH2 + H)+; HRMS (CI, NH3) m/z calcd for
C
16H15N6 (M + H)+ 291.1358, found 291.1363. Anal. Calcd
for C16H14N6: C, 66.19; H, 4.86; N, 28.95. Found: C, 65.93;
H, 5.15; N, 28.72.
1,14-Diiod o-3,6,9,12-t et r a oxa t et r a d eca n e (11). With
rapid stirring at 0 °C, I2 (30.4 g, 120 mmol) was slowly added
to pentaethylene glycol (10 g, 42 mmol), Ph3P (28.6 g, 109.1
mmol), and imidazole26 (7.8 g, 115 mmol) in MeCN (60 mL)
and Et2O (100 mL), resulting in a brown-black slurry. After
being stirred at 0 °C for 3 h, the mixture was diluted with
Et2O (900 mL), filtered, and washed with saturated aqueous
Na2S2O3 (3 × 225 mL), saturated aqueous CuSO4 (3 × 225
mL), and H2O (3 × 225 mL). The organic layer was dried,
filtered, and concentrated to give a white oily solid. Et2O (100
mL) was added, the resulting suspension was filtered, and the
filtrate was concentrated to give another white oily solid. This
procedure was repeated with Et2O (50 mL) to give a clear
slightly yellow oil. Chromatography (EtOAc-hexanes 1:2)
gave diiodide 11 (18.0 g, 94%) as a clear oil: Rf 0.42 (EtOAc-
2-Am in o-3-[(2-p yr id ylm eth ylen e)a m in o]-2(Z)-bu ten e-
1,4-d in itr ile (7). 2-Pyridinecarboxaldehyde (29.7 g, 280
mmol) was added to diaminomaleonitrile (6) (20.0 g, 185 mmol)
in MeOH (125 mL), and the mixture was stirred for 12 h when
a yellow solid precipitated out of solution. The solid was
collected by vacuum filtration and washed with Et2O-hexanes
(1:1) (500 mL) to yield imine 7 (31.9 g, 88%) as a light tan
solid: mp 195-197 °C; Rf 0.40 (EtOAc); IR (DRIFTS) νmax 3371,
2236, 2197, 1636, 1606, 1589, 1562 cm-1 1H NMR (CDCl3/
;
DMSO-d6, 270 MHz) δ 6.94-6.99 (1H, m), 7.15 (2H, br s),
7.35-7.42 (1H, m), 7.83 (1H, d, J ) 7.9 Hz), 7.95 (1H, s), 8.25
(1H, d, J ) 4.0 Hz); 13C NMR (DMSO, 75 MHz) δ 102.4, 113.8,
114.6, 122.4, 125.8, 128.7, 137.2, 150.1, 154.2, 155.1; MS (CI,
NH3) m/z 198 (M + H)+, 107 (M - PyrCH2 + 2H)+; HRMS
(CI, NH3) m/z calcd for C10H8N5 (M + H)+ 198.0778, found
198.0782. Anal. Calcd for C10H7N5: C, 60.91; H, 3.58; H,
35.51. Found: C, 60.62; H, 3.70; N, 35.32.
1
hexanes 1:1); IR (neat) νmax 1461, 1349, 1107 cm-1; H NMR
(CDCl3, 300 MHz) δ 3.19 (4H, t, J ) 7.0 Hz), 3.60 (12H, s),
3.69 (4H, t, J ) 7.0 Hz); 13C NMR (CDCl3, 75 MHz) δ 3.4, 70.6,
71.0, 71.1, 72.3; MS (CI, NH3) m/z 476 (M + NH4)+, 459 (M +
H)+, 177 (M - I - CH2CH2I + H)+; HRMS (CI, NH3) m/z calcd
for C10H24I2NO4 (M + NH4)+ 475.9795, found 475.9780.
2-Am in o-3-[(2-p yr id ylm eth yl)a m in o]-2(Z)-bu ten e-1,4-
d in itr ile (8). NaBH4 (3.9 g, 101.5 mmol) was slowly added
(25) For an overview of metal ion complexation by crown ethers and
related macrocycles, see: Lindoy, L. F. The Chemistry of Macrocyclic
Ligand Complexes; Cambridge University Press: 1989.
(26) Marshall, J . A.; Cleary, D. G. J . Org. Chem. 1986, 51, 858.

5814 J . Org. Chem., Vol. 63, No. 17, 1998
Beall et al.
3,18-Dia za -3,18-d iben zyl-1,2-d icya n o-6,9,12,15-tetr a ox-
a cycloocta d ecen e (12a ). A solution of dinitrile 10a 19 (7.2
g, 25 mmol) and diiodide 11 (11.45 g, 25 mmol) in dry DMF
(50 mL) was added with stirring over 8 h to Cs2CO3 (20.4 g,
62.5 mmol) in dry DMF (1200 mL) at 50 °C. After a further
24 h, the mixture was allowed to cool to room temperature
and stirred for 24 h. After the solvent was evaporated, EtOAc
(300 mL) was added to the residue. The organic suspension
was washed with water (2 × 100 mL) and brine (1 × 100 mL)
and the solvent evaporated. Chromatography (EtOAc-hex-
anes 1:1-1:0) gave dinitrile 12a (6.13 g, 50%) as a mixture of
geometrical isomers. Crystallization from EtOAc gave Z-
dinitrile 12a (3.1 g, 25%) as a yellow crystalline solid: mp 108-
110 °C (EtOAc); Rf 0.21 (EtOAc-hexanes 1:1); IR (CHCl3) νmax
dark blue solid: mp 190-193 °C; Rf 0.57 (CHCl3-MeOH 95:
5); IR (CHCl3) νmax 1572, 1549, 1121 cm-1; UV-vis (CHCl3)
λmax (log ꢀ) 326 (4.58), 358 (4.55), 562 (4.58), 668sh, 740sh nm;
1H NMR (CDCl3, 270 MHz) δ -1.03 (2H, s), 3.52-3.79 (64H,
br m), 4.45 (16H, br s), 5.40 (16H, s), 7.03-7.08 (24H, m), 7.37-
7.39 (16H, m); 13C NMR (CDCl3, 100 MHz) δ 50.6, 55.3, 70.2,
70.6, 70.8, 71.0, 126.3, 128.0, 128.5, 136.2, 140.6, 148.1;
FABMS m/z 1964 (M)+, 1873 (M - PhCH2)+, 1782 (M -
2PhCH2)+. Anal. Calcd for C112H138N16O16: C, 68.48; H, 7.08;
N, 11.41. Found: C, 68.58; H, 7.27; N, 11.38.
[Tet r a k is(1,16-d ia za -1,16-d ib en zyl-4,7,10,13-t et r a ox-
a cycloocta d ecen o)[14,15-b:14′,15′-g:14′′,15′′-l:14′′′,15′′′-q]-
p or p h yr a zin a to]n ick el(II) (1 (M ) Ni)). Porphyrazine 1
(M ) 2H) (40 mg, 0.02 mmol) and Ni(OAc)2 (50.7 mg, 0.204
mmol) in DMF (1.5 mL) and PhCl (4 mL) were heated at reflux
for 12 h and cooled to room temperature, and the blue
suspension was vacuum filtered through Celite and the solvent
evaporated. Chromatography (CHCl3-MeOH 100:0-97.5:2.5)
gave porphyrazine 1 (M ) Ni) (38 mg, 92%) as a dark blue
solid: mp 172-175 °C (CHCl3-MeOH); Rf 0.42 (CHCl3-MeOH
95:5); IR (CHCl3) νmax 1576, 1451, 1192 cm-1; UV-vis (CHCl3)
2201, 1579, 1496, 1125 cm-1 1H NMR (CDCl3, 270 MHz) δ
;
3.31 (4H, t, J ) 5.0 Hz), 3.59-3.69 (16H, m), 4.45 (4H, s), 7.11-
7.28 (10H, m); 13C NMR (CDCl3, 125 MHz) δ 50.9, 55.1, 69.2,
70.2, 70.6, 70.9, 115.3, 116.5, 127.5, 128.2, 128.6, 137.1; MS
(CI, NH3) m/z 491 (M + H)+, 401 (M - PhCH2)+, 91 (PhCH2)+;
HRMS (CI, NH3) m/z calcd for C28H35N4O4 (M + H)+ 491.2658,
found 491.2625. Anal. Calcd for C28H34N4O4: C, 68.55; H,
6.99; N, 11.42. Found: C, 68.53; H, 6.99; N, 11.41.
λ
max (log ꢀ) 312 (4.69), 380sh, 541 (4.51), 671 (4.41) nm; 1H NMR
3,18-Dia za -1,2-d icya n o-3,18-bis(2-p yr id ylm eth yl)-6,9,-
12,15-tetr a oxa cycloocta d ecen e (12b). Dinitrile 10b (7.25
g, 25.0 mmol) and diiodide 11 (11.5 g, 25.0 mmol) in dry DMF
(50 mL) were added over 8 h to a suspension of Cs2CO3 (20.4
g, 62.5 mmol) in dry DMF (1200 mL) at 50 °C. After the
addition was complete, the mixture was stirred at 50 °C for
24 h, allowed to cool to room temperature, and stirred for a
further 24 h. After evaporation, EtOAc (300 mL) was added
to the residue, which was washed with H2O (2 × 100 mL) and
brine (1 × 100 mL), and the solvent evaporated. Chromatog-
raphy (EtOAc-MeOH 95:5) gave dinitrile 12b (6.13 g, 55%)
as a mixture of geometrical isomers. Crystallization of this
mixture from EtOAc gave (Z)-12b (3.1 g, 30%) as a dark-yellow
crystalline solid: mp 194-196 °C (EtOAc); Rf 0.18 (EtOAc-
MeOH 95:5); IR (CHCl3) νmax 2201, 1589, 1123 cm-1; 1H NMR
(CDCl3, 270 MHz) δ 3.42 (4H, t, J ) 5.0 Hz), 3.61-3.70 (16H,
m), 4.62 (4H, s), 7.10-7.16 (4H, m), 7.55-7.62 (2H, m), 8.42-
8.44 (2H, m); 13C NMR (CDCl3, 75 MHz) δ 51.6, 56.0, 69.3,
70.3, 70.7, 71.0, 115.5, 116.4, 122.3, 122.4, 136.6, 149.5, 157.5;
MS (CI, NH3) m/z 493 (M + H)+, 402 (M - PyrCH2 + H)+, 94
(PyrCH2 + 2H)+; HRMS (CI, NH3) m/z calcd for C26H33N6O4
(M + H)+ 493.2565, found 493.2584. Anal. Calcd for
(CDCl3, 300 MHz) δ 3.55-3.81 (64H, m), 4.44 (16H, br s), 5.39
(16H, s), 7.09-7.15 (24H, m), 7.41-7.43 (16H, m); 13C NMR
(CDCl3, 100 MHz) δ 50.8, 55.8, 70.2, 70.6, 70.8, 70.9, 126.4,
128.1, 128.5, 137.3, 140.7, 143.4; FABMS m/z 2020 (M)+, 1010
(M)2+. Anal. Calcd for C112H136N16NiO16: C, 66.56; H, 6.78;
N, 11.09. Found: C, 66.48; H, 6.69; N, 10.80.
[Tetr a k is[1,16-d ia za -1,16-bis(2-p yr id ylm eth yl)-4,7,10,-
13-t et r a oxa cyclooct a d ecen o][14,15-b:14′,15′-g:14′′,15′′-l:
14′′′,15′′′-q]p or p h yr a zin a to]m a gn esiu m (II) [2 (M ) Mg)].
Mg turnings (5.3 mg, 0.22 mmol), a crystal of I2, and 1-butanol
(5 mL) were heated at reflux for 24 h and cooled to room
temperature when dinitrile 12b (220 mg, 0.44 mmol) was
added and the solution heated at reflux for a further 24 h.
After being allowed to cool to room temperature, the mixture
was diluted with CHCl3 (6 mL) and vacuum filtered through
Celite and the solvent evaporated. Chromatography (CHCl3-
MeOH-NH4OH 97.25:2.5:0.25-83.5:15:1.5) gave porphyrazine
2 (M ) Mg) (35 mg, 16%) as a dark green solid: mp 115-118
°C; Rf 0.16 (CHCl3-MeOH-NH4OH) 94:5:1); IR (CHCl3) νmax
1591, 1569, 1108 cm-1; UV-vis (CHCl3) λmax (log ꢀ) 257 (4.54),
342 (4.58), 580 (4.25), 664 (4.29) nm; 1H NMR (CDCl3, 400
MHz) δ 2.90-3.86 (64H, m), 4.06-4.64 (16H, m), 5.56 (16H,
br s), 6.61-7.98 (24H, m), 8.26-8.93 (8H, m); 13C NMR (CDCl3,
100 MHz) δ 51.8, 58.1, 69.7, 70.1, 70.4, 70.6, 121.4, 122.6,
136.3, 137.1, 148.7, 152.1, 160.7; FABMS m/z 1995 (M + H)+.
2,3-Bis[m et h yl(2-p yr id ylm et h yl)a m in o]-2(Z)-b u t en e-
1,4-d in itr ile (13). Dinitrile 10b (1.0 g, 3.5 mmol) in 1,2-
dimethoxyethane (DME) (10 mL) was added to a cooled (-22
°C) suspension of NaH (60% dispersion in mineral oil; 350 mg,
8.6 mmol) in DME (10 mL). After 30 min, Me2SO4 (1.0 g, 7.9
mmol) in DME (5 mL) was added, and the brown mixture was
cooled to -45 °C and then allowed to warm slowly to room
temperature. H2O (5 mL) was carefully added and the
aqueous layer extracted with EtOAc (3 × 30 mL). The
combined organic layers were washed with H2O (2 × 25 mL)
and brine (1 × 25 mL), dried, and evaporated. Chromatog-
raphy (EtOAc to EtOAc-MeOH 97.5:2.5) gave dinitrile 13 (780
mg, 71%) as a brown oil: Rf 0.23 (EtOAc-MeOH 95:5); IR
C
26H32N6O4: C, 63.40; H, 6.55; N, 17.06. Found: C, 63.51; H,
6.25; N, 16.99.
[Tet r a k is(1,16-d ia za -1,16-d ib en zyl-4,7,10,13-t et r a ox-
a cycloocta d ecen o)[14,15-b:14′,15′-g:14′′,15′′-l:14′′′,15′′′-q]-
p or p h yr a zin a to]m a gn esiu m (II) [1 (M ) Mg)]. Mg turn-
ings (12.4 mg, 0.51 mmol), a crystal of I2, and 1-butanol (20
mL) were heated at reflux for 24 h. After the mixture was
cooled to room temperature, dinitrile 12a (500 mg, 1.02 mmol)
was added and the solution heated at reflux for a further 36
h. After being allowed to cool to room temperature, the
mixture was diluted with CHCl3 (20 mL), vacuum filtered
through Celite, and evaporated. Chromatography (EtOAc-
MeOH 99:1-95:5) gave porphyrazine 1 (M ) Mg) (125 mg,
25%) as a dark blue solid: mp 187-190 °C; Rf 0.34 (CHCl3-
MeOH 95:5); IR (CHCl3) νmax 1559, 1453, 1290, 1115 cm-1
;
UV-vis (CHCl3) λmax (log ꢀ) 334 (4.67), 363 (4.71), 566 (4.37),
709 (4.58) nm; 1H NMR (CDCl3, 270 MHz) δ 2.90-3.90 (64H,
br m), 4.20-4.60 (16H, br m), 5.20-5.60 (16H, br m), 6.70-
7.60 (40H, br m); 13C NMR (CDCl3, 75 MHz) δ 51.9, 56.3, 71.1,
126.5, 128.4, 128.6, 137.5, 141.8, 152.6; FABMS m/z 1986 (M)+,
1
(neat) νmax 2185, 1591, 761 cm-1; H NMR (CDCl3, 300 MHz)
δ 2.83 (6H, s), 4.40 (4H, s), 7.16-7.28 (4H, m), 7.64-7.69 (2H,
m), 8.53-8.56 (2H, m); 13C NMR (CDCl3, 75 MHz) δ 41.8, 60.2,
45.5, 118.2, 123.3, 123.4, 137.5, 150.4, 157.0; MS (CI, NH3)
993 (M)2+
.
Anal. Calcd for C112H136MgN16O16: C, 67.71; H,
m/z 319 (M + H)+, 228 (M - PyrCH2 + 2H)+, 94 (PyrCH2
+
6.90; N, 11.28. Found: C, 67.71; H, 6.90; N, 11.08.
2H)+; HRMS (CI, NH3) m/z calcd for C18H19N6 (M + H)+
319.1671, found 319.1686. Anal. Calcd for C18H18N6: C, 67.91;
H, 5.70; N, 26.40. Found: C, 67.94; H, 5.48; N, 26.15.
[2,3,7,8,12,13,17,18-Octa [m eth yl(2-p yr id ylm eth yl)a m i-
n o]p or p h yr a zin a to]m a gn esiu m (II) (4). Dry 1-propanol (5
mL) and a crystal of I2 were added to Mg turnings (10 mg,
0.41 mmol), and the suspension was heated at reflux for 24 h.
After the mixture was cooled to room temperature, dinitrile
13 (350 mg, 1.10 mmol) in dry 1-propanol (2 mL) was added.
The resulting suspension was heated at reflux for 24 h, cooled
Tetr a k is(1,16-d ia za -1,16-d iben zyl-4,7,10,13-tetr a oxa cy-
cloocta d ecen o)[14,15-b:14′,15′-g:14′′,15′′-l:14′′′,15′′′-q]p or -
p h yr a zin e [1 (M ) 2H)]. In the dark, CF3CO2H (2 mL) was
added to porphyrazine 1 (M ) Mg) (107 mg, 0.054 mmol), and
after 20 min, the solution was added to rapidly stirring ice-
H2O (50 mL) and neutralized with 1 M NaOH. The suspension
was vacuum filtered through Celite, and the solids were
washed with distilled water. Chromatography (CHCl3-MeOH
97.5:2.5) gave porphyrazine 1 (M ) 2H) (101 mg, 95%) as a

Porphyrazines and Norphthalocyanines
J . Org. Chem., Vol. 63, No. 17, 1998 5815
to room temperature, diluted with CHCl3 (10 mL), and filtered
through Celite and the solvent evaporated. Chromatography
(CHCl3-MeOH-NH4OH 94:5:1) followed by gel permeation
chromatography on Bio-Beads S-X3 (CHCl3) gave porphyrazine
4 (45 mg, 13%) as a dark blue solid: mp 92-95 °C; IR (CHCl3)
νmax 1571, 1473, 1434 cm-1; UV-vis (CHCl3), λmax (log ꢀ) 258
(4.48), 352, (4.65), 531, (4.16), 702 (4.48) nm; 1H NMR (CDCl3,
300 MHz) δ 3.56 (24H, br s), 5.09 (16H, br s), 6.84-6.86 (8H,
m), 7.22-7.31 (16H, m), 7.94 (8H, br s); 13C NMR (CDCl3, 100
MHz) δ 42.9, 61.5, 121.5, 122.2, 136.4, 138.3, 148.4, 152.4,
160.2; FABMS m/z 1298 (M)+, 1259 (M - Mg - Me)+, 1071
(M - Mg - Me - 2(PyrCH2))+.
blue solid: mp 186-189 °C; Rf 0.35 (EtOAc-hexanes 1:3); IR
(CHCl3) νmax 1551, 1496, 1453, 1320, 1108, 1016 cm-1; UV-
vis (CHCl3) λmax (log ꢀ) 299 (4.59), 345 (4.91), 527sh, 602sh,
1
658 (4.65), 688sh, 733 (4.69) nm; H NMR (CDCl3, 300 MHz)
δ -0.65 (2H, br s), 1.10-1.20 (18H, m), 1.67-1.77 (12H, m),
1.97 (12H, br s), 3.12 (12H, br s), 3.60 (12H, app d), 4.06 (4H,
br s), 4.81 (4H, br s), 5.85 (4H, s), 7.28-7.37 (6H, m), 7.71 (4H,
d, J ) 7.2 Hz), 8.69 (2H, s), 9.01 (2H, s), 9.19 (2H, s); 13C NMR
(CDCl3, 100 MHz) δ 14.2, 23.1, 23.2, 33.5, 33.6, 33.8, 33.9, 34.0,
34.1, 52.3, 57.5, 70.35, 70.44, 70.7, 70.8, 122.5, 122.9, 123.4,
126.6, 128.2, 128.6, 132.3, 134.2, 137.5, 138.3, 140.2, 140.7,
142.69, 142.73, 143.3, 144.5, 156.1, 159.3; FABMS m/z 1212
(M)+, 1122 (M - PhCH2 + H)+, 1031 (M - 2(PhCH2) + H)+,
91 (PhCH2)+; HRFABMS m/z calcd for C76H97N10O4 (M + H)+
1213.7694, found 1213.7705. Anal. Calcd for C76H96N10O4: C,
75.21; H, 7.97; N, 11.54. Found: C, 74.95; H, 7.91; N, 11.25.
[2,3-[14′,15′-(1′,16′-Dia za -1′,16′-b is(2-p yr id ylm et h yl)-
4′,7′,10′,13′-t et r a oxa cyclooct a d ecen o)]-9,10,18,19,27,29-
h exa bu tyln or p h th a locya n a to]m a n ga n ese(III) Ch lor id e
(3). MnBr2 (3.0 mg, 1.4 µmol) and 2,6-lutidine (1 drop) were
added to a suspension of norphthalocyanine 15a (11 mg, 9
µmol) in DMF (3 mL). The resulting suspension was heated
at 100 °C for 2 h. After the suspension was cooled to room
temperature, brine (4 mL) was added to the dark green
solution and the mixture was stirred for 1 h, poured into H2O
(3 mL) and extracted with CHCl3 (3 × 10 mL). Evaporation
and chromatography (CHCl3-MeOH 90:10) gave norphthalo-
cyanine 3 (11 mg, 94%) as a dark green solid: mp 87-90 °C;
Rf 0.43 (CHCl3-MeOH 90:10); IR (CHCl3) νmax 1563, 1466,
1337, 1101, 750 cm-1; UV-vis (CHCl3) λmax (log ꢀ) 279 (4.74),
367sh, 381 (4.64), 524 (4.20), 661sh, 730 (4.50) nm; FABMS
m/z 1267 (M - Cl)+, 1176 (M - Cl - (PyrCH2) + 2H)+, 634
(M)2+; HRFABMS m/z calcd for C74H92N12O4Mn (M - Cl)+
1267.674, found 1267.683. Anal. Calcd for C74H92ClMn-
2,3-[14′,15′-[1′,16′-Diaza-1′,16′-bis(2-pyr idylm eth yl)-4′,7′,-
10′,13′-tetr aoxacyclooctadecen o]]-9,10,18,19,27,29-h exabu -
tyln or p h th a locya n in e [15a (M ) 2H)]. A rapidly stirred
mixture of Mg turnings (23 mg, 0.91 mmol), 1-butanol (8.0 mL),
and I2 (1 crystal) was heated at reflux for 24 h. Solid I2 was
slowly added to this refluxing mixture until a uniform white
suspension was obtained. Dinitrile 1422 (500 mg, 2.1 mmol)
and dinitrile 12b (210 mg, 0.42 mmol) were added to the
suspension at room temperature, which was heated at reflux
for 24 h and then allowed to cool to room temperature. After
evaporation, CH2Cl2 (25 mL) was added, and the resulting
blue-green suspension was vacuum-filtered through Celite and
concentrated to give the crude magnesium norphthalocyanine
15a (M ) Mg) as a dark gummy solid. CF3CO2H (7.5 mL)
was added to the crude residue, which was allowed to stand
protected from light for 2 h, added to ice-H2O (100 mL) and
neutralized with 1 M NaOH. The resulting suspension was
extracted with CHCl3 (3 × 25 mL), and the combined organic
layers were dried, filtered, and concentrated to yield the crude
2H-norphthalocyanine. The residue was chromatographed
twice (MeOH-CHCl3 0:100-5:95; hexanes (60-80 °C)-
acetone-NH4OH 80:19:1 to 75:24:1 dried over CaCl2) to give
norphthalocyanine 15a (M ) 2H) (54 mg, 11%) as a dark blue
solid: mp 182-185 °C; Rf 0.33 (CHCl3-MeOH 95:5); IR
(CHCl3) νmax 1553, 1321, 1108, 1016 cm-1; UV-vis (CHCl3) λmax
(log ꢀ) 299 (4.60), 345 (4.92), 519sh, 590sh, 654 (4.67), 685sh,
730 (4.75) nm; 1H NMR (CDCl3, 300 MHz) δ -0.44 (2H, br s),
1.12-1.18 (18H, m), 1.64-1.76 (12H, m), 1.88-2.01 (12H, m),
3.10-3.23 (12H, m), 3.55 (4H, s), 3.61-3.67 (8H, m), 4.14 (4H,
br s), 4.89 (4H, br s), 5.93 (4H, s), 7.04 (2H, app t), 7.36 (2H,
app t), 7.63 (2H, d, J ) 7.8 Hz), 8.57 (2H, d, J ) 4.3 Hz), 8.71
(2H, s), 9.07 (2H, s), 9.33 (2H, s); 13C NMR (CDCl3, 125 MHz)
δ 14.2, 23.1, 23.18, 23.20, 33.5, 33.6, 33.7, 33.8, 34.0, 34.1, 53.0,
59.4, 70.3, 70.4, 70.6, 70.8, 121.6, 122.6, 122.7, 122.9, 123.3,
132.3, 133.8, 136.2, 137.5, 138.2, 140.6, 142.7, 142.8, 143.7,
144.5, 149.0, 155.9, 159.3, 160.4; FABMS m/z 1215 (M + H+),
1123 (M - (2-Pyr)CH2 + H)+, 1031 (M - 2((2-Pyr)CH2 + H)+,
93 ((2-Pyr)CH2 + H)+; HRFABMS m/z calcd for C74H95N12O4
N
12O4‚CHCl3: C, 63.29; H, 6.59; N, 11.81. Found: C, 63.52;
H, 6.71; N, 11.96.
2,3-Bis[m eth yl(2-p yr id ylm eth yl)a m in o]-9,10,18,19,27,-
28-h exa bu tyln or p h th a locya n in e [5 (M ) 2H)]. A rapidly
stirring mixture of Mg turnings (30 mg, 1.2 mmol), 1-butanol
(10.0 mL), and I2 (1 crystal) was heated at reflux for 24 h.
Further I2 was slowly added to this refluxing mixture until a
uniform white suspension was obtained. Dinitrile 14 (670 mg,
2.8 mmol), as a solid, and dinitrile 13 (180 mg, 0.56 mmol), as
a solution in 1-butanol (1 mL), were added at room tempera-
ture, and the suspension was heated at reflux for 24 h and
allowed to cool to room temperature. After evaporation, CH2-
Cl2 (25 mL) was added, and the resulting blue-green suspen-
sion was vacuum-filtered through Celite and concentrated to
give the crude magnesium norphthalocyanine 5 (M ) Mg) as
a dark gummy solid. CF3CO2H (7.5 mL) was added, and the
solution was allowed to stand protected from light for 2 h,
added to ice-H2O (100 mL), and neutralized with 1 M NaOH.
The resulting suspension was extracted with CHCl3 (3 × 25
mL), and the combined organic layers were dried, filtered, and
concentrated to yield the crude 2H-norphthalocyanine. The
residue was chromatographed twice (MeOH-CHCl3 0:100-
5:95; hexanes (60-80 °C)-acetone-NH4OH 80:19:1-75:24:1
dried over CaCl2) to give norphthalocyanine 5 (M ) 2H) (58
mg, 10%) as a dark blue solid: mp 172-175 °C; Rf 0.35
(CHCl3-MeOH) 90:10); IR (CHCl3) νmax 1571, 1321, 1110, 1012
(M + H)+ 215.7559, found 1215.7589. Anal. Calcd for C74H94
12O4: C, 73.12; H, 7.79; N, 13.83. Found: C, 73.22; H, 7.61;
N, 13.70.
-
N
2,3-[14′,15′-(1′,16′-Dia za -1′,16′-d ib en zyl-4′,7′,10′,13′-t et -
r a oxa cyclooct a d ecen o)]-9,10,18,19,27,29-h exa b u t yln or -
p h th a locya n in e [15b (M ) 2H)]. A rapidly stirring mixture
of Mg turnings (35 mg, 1.4 mmol), 1-butanol (11.5 mL), and I2
(1 crystal) was heated at reflux for 24 h, when further I2 was
slowly added to this refluxing mixture until a uniform white
suspension was obtained. At room temperature, dinitriles 1422
(750 mg, 3.1 mmol) and 12a (310 mg, 0.63 mmol) were added
as solids to the suspension, which was heated at reflux for 24
h and then allowed to cool to room temperature. After
evaporation, CH2Cl2 (25 mL) was added, and the resulting
blue-green suspension was vacuum-filtered through Celite and
concentrated to give the crude magnesium norphthalocyanine
15b (M ) Mg) as a dark gummy solid. CF3CO2H (7.5 mL)
was added to the crude residue, and the mixture was allowed
to stand protected from light for 2 h, added to ice-H2O (100
mL), and neutralized with 1 M NaOH. The resulting suspen-
sion was extracted with CHCl3 (3 × 25 mL), and the combined
organic layers were dried, filtered, and concentrated to yield
the crude 2H-norphthalocyanine. The residue was chromato-
graphed twice (CHCl3; EtOAc-hexanes (60-80 °C) 1:4-1:3)
to give norphthalocyanine 15b (M ) 2H) (68 mg, 9%) as a dark
cm-1 1H NMR (CDCl3, 300 MHs) δ -1.25 (2H, br s), 1.13-
;
1.21 (18H, m), 1.58-1.79 (12H, m), 1.89-2.00 (12H, m), 2.97-
3.18 (12H, m), 3.88 (6H, s), 5.97 (4H, s), 7.18 (2H, app t), 7.51
(2H, app t), 7.60 (2H, d, J ) 7.7 Hz), 8.29 (2H, s), 8.71 (2H, d,
J ) 4.5 Hz), 8.85 (2H, s), 9.15 (2H, s); 13C NMR (CDCl3, 100
MHz) δ 14.2, 23.3, 33.6, 33.8, 33.9, 34.1, 42.4, 62.4, 121.8,
122.5, 122.6, 122.7, 123.3, 132.3, 134.5, 136.4, 137.3, 138.0,
142.5, 142.7, 144.4, 149.2, 155.7, 158.9, 160.2 (C(Pyr)); FABMS
m/z 1041 (M + H),+ 920 (M - 2(CH3) - PyrCH2 + 2H)+, 829
(M - 2(CH3) - 2(PyrCH2) + 3H)+, 93 (PyrCH2 + H)+;
HRFABMS m/z calcd for C66H81N12 (M + H)+ 1041.6707, found
1041.6660. Anal. Calcd for C66H80N12: C, 76.12; H, 7.74; N,
16.14. Found: C, 76.41; H, 7.53; N, 15.87.
[2,3-Bis[m eth yl(2-p yr id ylm eth yl)a m in o]-9,10,18,19,27,-
28-h exa bu tyln or p h th a locya n a to]m a n ga n ese(III) Ch lo-

5816 J . Org. Chem., Vol. 63, No. 17, 1998
Ta ble 3. Cr ysta l Da ta , Da ta Collection , a n d Refin em en t P a r a m eter sa
Beall et al.
data
12a
1 (M ) Mg)
12b‚Cu(BF4)2
12b‚(HClO4)2
formula
solvent
formula wt
color, habit
cryst size/mm
cryst syst
C28H34N4O4
C112H136N16O17Mg
0.75EtOAc
2068.8
deep red blocks
0.43 × 0.33 × 0.27
monoclinic
P21/n, 14
C26H32N6O4Cu‚2BF4
C26H34N6O4Cu‚2ClO4
q
490.6
729.7
693.5
yellow cubes
0.37 × 0.33 × 0.33
monoclinic
C2/c, 15
deep blue plates
0.40 × 0.37 × 0.20
monoclinic
P21, 4
pale yellow needles
0.57 × 0.08 × 0.07
monoclinic
P21/c, 14
space grp symbol, no.
T/K
293
203
293
293
cell dimensions
a/Å
b/Å
14.203(3)
11.753(3)
16.923(5)
112.13(2)
2617(1)
4 [b]
24.419(9)
17.824(8)
25.512(10)
99.43(3)
10954(7)
4
8.082(3)
9.797(3)
20.206(11)
96.84(4)
1589(1)
2
19.714(5)
8.041(1)
21.380(5)
112.62(2)
3129(1)
4
c/Å
â/deg
V/Å3
Z
Dc/g cm-3
1.245
1.254
1.526
1.472
F(000)
1048
Cu KR
0.68
4416
746
Cu KR
1.78
1448
radiatn used
Cu KRc
0.75
Cu KRc
2.50
µ/mm-1
θ range/deg
no. of unique reflns
measured
5.1-62.5
2.3-56.1
2.2-62.5
2.4-60.0
2097
1799
14288
7682
2801
2717
Gaussian
0.71, 0.52
425
0.055
0.150
0.098, 1.530
0.57, -0.57
4625
3788
obsd, |Fo| > 4σ(|Fo|)
absorptn correctn
max, min transmission
no. of variables
∧c
152
0.093
0.255
0.186, 2.484
0.51, -0.44
1328
424
0.049
0.131
0.074, -0.35
0.52, -0.35
d
R1
0.148
0.402
0.301, 22.245
0.85, -0.58
e
wR2
weighting factors a, bf
largest diff peak, hole/e Å-3
a
b
Details in common: graphite monochromated radiation, ω scans, Siemens P4 diffractometer, refinement based on F2. The molecule
has crystallographic C2 symmetry. c Rotating anode source. R1 ) ∑||Fo| - |Fc||/∑|Fo|. e wR2 ) x{∑[w(Fo - Fc2)2]/∑[w(Fo2)2]}. f w-1
)
d
2
σ2(Fo2) + (aP)2 + bP.
r id e [5 (M ) Mn Cl)]. MnBr2 (10 mg, 4.7 µmol) and 2,6-
lutidine (1 drop) were added to a suspension of norph-
thalocyanine 5 (M ) 2H) (25 mg, 2.4 µmol) in DMF (10 mL),
and the mixture was heated at 100 °C for 2.5 h. After the
mixture was cooled to room temperature, brine (5 mL) was
added to the dark green solution, and the mixture was allowed
to stir at room temperature for 1 h. The mixture was poured
into H2O (10 mL) and extracted with CHCl3 (3 × 10 mL) and
the extract evaporated. Chromatography (CHCl3-MeOH 95:
5) gave norphthalocyanine 5 (M ) MnCl) (23 mg, 85%) as a
dark green solid: mp 230-233 °C; Rf 0.43 (CHCl3-MeOH 95:
5); IR (CHCl3) νmax 1567, 1335, 745 cm-1; UV-vis (CHCl3) λmax
(log ꢀ) 279 (4.70), 367sh, 381 (4.60), 521 (4.15), 684sh, 737
(4.48) nm; FABMS m/z 1093 (M - Cl)+, 1002 (M - Cl -
(PyrCH2) + H)+, 909 (M - Cl - 2(PyrCH2) + H)+; HRFABMS
m/z calcd for C66H78N12Mn (M - Cl)+ 1093.585, found 1093.589.
Anal. Calcd for C66H78ClMnN12: C, 70.16; H, 6.96; N, 14.88.
Found: C, 69.99; H, 7.09; N, 14.58.
Gen er a l P r oced u r e for UV-vis Titr a tion s of P or -
p h yr a zin es 1, 2, a n d 4 a n d Nor p h th a locya n in es 3 a n d 5.
CHCl3 solutions of known concentration of porphyrazine or
norphthalocyanine (3 mL) were subject to UV-vis titrations
with MeOH solutions of varying concentrations (0, 0.25, 0.5,
1, 2, 3, 4, 6, 8, 20, 40, >100 molar equiv) of the metal salt of
interest. For each titration, the solvent ratio was always
CHCl3:MeOH ) 3:1. Blank UV-vis spectra (in the absence
of metal salt) were run for each of the porphyrazines and
norphthalocyanines to determine any solvent effect (of which
there were none). Blank UV-vis spectra (in the absence of
porphyrazine or norphthalocyanine) were also run for each
metal salt to make sure that there was no significant absor-
bance in the window of interest (300-850 nm).
m/z calcd for C26H32N6O4Cu 555.1781, found 555.1815. Anal.
Calcd for C26H32B2CuF8N6O4: C, 42.79; H, 4.42; N, 11.52.
Found: C, 42.57; H, 4.24; N, 11.35.
Com p lex 12b‚(HClO4)2. A solution of dinitrile 12b (20 mg,
40 µmol) in MeOH (1 mL) was added to a solution of HClO4
(12 mg, 120 µmol) in MeOH (1 mL). The layers were mixed
and allowed to stand at room temperature to provide 12b‚
(HClO4)2 as a pale yellow crystalline solid: mp 93-95 °C; IR
(DRIFTS) νmax 2193, 1617, 1098, 767, 623 cm-1; FABMS m/z
493 (M + H)+, 402 (M - PyrCH2 + 2H)+, 93 (PyrCH2 + H)+;
HRFABMS m/z calcd for C26H33N6O4 (M + H)+ 493.2563, found
493.2580. Anal. Calcd for C26H34Cl2N6O12: C, 45.03; H, 4.93;
N, 12.12. Found: C, 45.05; H, 4.99; N, 12.11.
([2,3-Bis[m et h yl(2-p yr id ylm et h yl)a m in o]-9,10,18,19,-
27,28-hexabutylnorphthalocyanato]manganese(III)chloride)‚
Cop p er (II) Aceta te (16a ). Slow evaporation of a solution of
norphthalocyanine 5 (M ) MnCl) (6 mg, 5.3 µmol) and Cu-
(OAc)2‚H2O (1.1 mg, 5.3 µmol) in CHCl3 and MeOH (1:1, 6 mL)
gave complex 16a as a dark green solid: mp 128-130 °C; IR
(DRIFTS) νmax 1573, 1459, 1337, 1048, 749 cm-1; UV-vis
(CHCl3/MeOH 3:1) λmax (log ꢀ) 267 (4.67), 284sh, 367sh, 390
(4.58), 607sh, 656 (4.43), 733 (4.60) nm; FABMS m/z 1193 (M
- 2(CH3CO2))+, 1156 (M - Cl - 2(CH3CO2))+, 1093 (M - Cl -
Cu - (2CH3CO2))+, 578 (M - Cl - 2(CH3CO2))2+; HRFABMS
m/z calcd for C66H78N12ClMnCu (M - 2(CH3CO2))+ 1191.484,
found
1191.486.
Anal.
Calcd
for
C70H84ClCu-
MnN12O4: C, 64.11; H, 6.46; N, 12.82. Found: C, 64.23; H,
6.16; N, 12.69.
([2,3-Bis[m et h yl(2-p yr id ylm et h yl)a m in o]-9,10,18,19,-
27,28-hexabutylnorphthalocyanato]manganese(III)chloride)‚
Coba lt(II) Ch lor id e (16b). Slow evaporation of a solution
of norphthalocyanine 5 (M ) MnCl) (6 mg, 5.3 µmol) and CoCl2
(0.7 mg, 5.3 µmol) in CHCl3 and MeOH (1:1, 6 mL) gave
complex 16b as a dark green solid: mp dec; IR (DRIFTS) νmax
1461, 1337, 1046, 753 cm-1; UV-vis (CHCl3-MeOH 1:1) λmax
(log ꢀ) 281 (4.77), 373sh, 386 (4.72), 615sh, 664 (4.57), 735
(4.74) nm; FABMS m/z 1224 (M - Cl)+, 1187 (M - 2Cl)+. Anal.
Com p lex 12b‚Cu (BF 4)2. A solution of dinitrile 12b (10 mg,
20 µmol) in MeOH (1 mL) was added to a solution of Cu(BF4)2‚
xH2O (25 mg, 70 µmol) in MeOH (1 mL). The layers were
mixed and allowed to stand at room temperature. Complex
12b‚Cu(BF4)2 was obtained as a dark blue crystalline solid:
mp > 190 °C dec; IR (DRIFTS) νmax 2227, 1613, 1448, 1057
cm-1; FABMS m/z 555 (M)+, 493 (M - Cu + H)+; HRFABMS
Calcd for C66H78Cl3CoMnN12
: C, 62.93; H, 6.24; N, 13.34.
Found: C, 62.68; H, 5.95; N, 13.48.

Porphyrazines and Norphthalocyanines
J . Org. Chem., Vol. 63, No. 17, 1998 5817
Table 3 provides a summary of the crystal data, data
collection, and refinement parameters for 12a , 1 (M ) Mg),
12b‚Cu(BF4)2, and 12b‚(HClO4)2. The structures were solved
by direct methods and were refined by full-matrix least-
squares [blocked in the case of 1 (M ) Mg)] on the basis of F2.
In 1 (M ) Mg), disorder was found in the polyether chain of
ring D, and this was resolved into two 50:50 partial occupancy
orientations. In all four structures, all of the non-hydrogen
atoms were refined anisotropically [including the 75% oc-
cupancy ethyl acetate solvent molecule in 1 (M ) Mg)] with,
in 12a and 1 (M ) Mg), the pendant phenyl rings being refined
as optimized rigid bodies. In 12b‚(HClO4)2, the N-H hydrogen
atoms were located from a ∆F map and refined isotropically
subject to an N-H distance constraint. The C-H hydrogen
atoms in each structure were placed in calculated positions,
assigned isotropic thermal parameters, U(H) ) 1.2Ueq(C) [U(H)
) 1.5Ueq(CMe)], and allowed to ride on their parent atoms.
Computations were carried out using the SHELXTL PC
program system.27 The absolute structure of 12b‚Cu(BF4)2 was
determined by use of the Flack parameter, which refined to a
value of 0.06(7).
Ack n ow led gm en t. We thank GlaxoWellcome for
the generous endowment (A.G.M.B.), the Wolfson Foun-
dation for establishing the Wolfson Centre for Organic
Chemistry in Medical Science at Imperial College, the
Engineering and Physical Sciences Research Council,
the National Science Foundation (CHE-9408651), and
NATO for generous support of our studies.
Su p p or tin g In for m a tion Ava ila ble: Copies of the 1H
(300 MHz, CDCl3) and 13C (75 MHz, CDCl3) NMR spectra of
diiodide 11 and porphyrazines 2 (M ) Mg) and 4; X-ray data
for 12a , 1 (M ) Mg), 12b‚Cu(BF4)2, and 12b‚(HClO4)2; and
UV-vis titrations of ligand 1 (M ) Ni) with Hg(ClO4)2, ligand
2 with AgBF4, Pb(NO3)2, CuCl2, CoCl2, Zn(ClO4)2, and CdCl2,
ligand 3 with Cu(OAc)2, Hg(ClO4)2, AgBF4, Zn(ClO4)2, Co(BF4)2,
and CdCl2, ligand 4 with CuCl2, Zn(ClO4)2, Hg(ClO4)2, CdCl2,
and AgBF4, and ligand 5 with CdCl2, Co(BF4)2, Zn(ClO4)2, and
Hg(ClO4)2 (49 pages). This material is contained in libraries
on microfiche, immediately follows this article in the microfilm
version of the journal, and can be ordered from the ACS; see
any current masthead page for ordering information.
(27) SHELXTL PC version 5.03, Siemens Analytical X-ray Instru-
ments, Inc., Madison, WI, 1994.
J O9802574