High fidelity self-sorting assembling of meso-cinchomeronimide appended meso-meso linked Zn(II) diporphyrins

Article abstract of DOI:10.1021/ja0611137

In noncoordinating solvents, meso-cinchomeronimide appended Zn(II) porphyrin 2 forms a cyclic trimer, while diporphyrins 7 exhibit high-fidelity self-sorting assembling to form discrete cyclic trimer, tetramer, and pentamer with large association constants from 7_in-in, 7_in-out, and 7_out-out, respectively, through almost perfect discrimination of enantiomeric and conformational differences of the mesocinchomeronimide substituents. In the latter self-sorting processes, the dihedral angles dictated by the two pyridyl nitrogen atoms control the size of the aggregates; the trimer from 7_in-in, the tetarmer from 7_in-out, and the pentamer from 7_out-out. Cyclic structures of (2)₃ and (R-7_out-out)₅ have been determined by single-crystal X-ray diffraction analysis.

Full text of DOI:10.1021/ja0611137

Published on Web 05/17/2006
High Fidelity Self-Sorting Assembling of
meso-Cinchomeronimide Appended meso-meso Linked Zn(II)
Diporphyrins
Taisuke Kamada,† Naoki Aratani,† Toshiaki Ikeda,† Naoki Shibata,‡
Yoshiki Higuchi,*,‡ Atsushi Wakamiya,§ Shigehiro Yamaguchi,§ Kil Suk Kim,|
Zin Seok Yoon,| Dongho Kim,*,| and Atsuhiro Osuka*,†
Contribution from the Department of Chemistry, Graduate School of Science, Kyoto UniVersity,
and CREST (Core Research for EVolutional Science and Technology) of Japan Science and
Technology Agency, Sakyo-ku, Kyoto 606-8502, Japan, Graduate School of Life Science,
UniVersity of Hyogo, 3-2-1 Koto, Kamigori-cho, Ako-gun, Hyogo 678-1297, Japan, and RIKEN
Harima Institute/SPring-8, 1-1-1 Koto, Mikazuki-cho, Sayo-gun, Hyogo 679-5248, Japan,
Department of Chemistry, Graduate School of Science, Nagoya UniVersity, Chikusa,
Nagoya 464-8602, Japan, and Center for Ultrafast Optical Characteristics Control and
Department of Chemistry, Yonsei UniVersity, Seoul 120-749, Korea
Received February 15, 2006; E-mail: osuka@kuchem.kyoto-u.ac.jp; dongho@yonsei.ac.kr; hig@sci.u-hyogo.ac.jp
Abstract: In noncoordinating solvents, meso-cinchomeronimide appended Zn(II) porphyrin 2 forms a cyclic
trimer, while diporphyrins 7 exhibit high-fidelity self-sorting assembling to form discrete cyclic trimer, tetramer,
and pentamer with large association constants from 7in-in, 7in-out, and 7out-out, respectively, through almost
perfect discrimination of enantiomeric and conformational differences of the meso-cinchomeronimide
substituents. In the latter self-sorting processes, the dihedral angles dictated by the two pyridyl nitrogen
atoms control the size of the aggregates; the trimer from 7in-in, the tetarmer from 7in-out, and the pentamer
from 7out-out. Cyclic structures of (2)3 and (R-7out-out)5 have been determined by single-crystal X-ray diffraction
analysis.
central metal ions with coordinating sidearms.6,7 However, such
metalloporphyrins have been scarcely tested for self-sorting
Introduction
Self-sorting is high fidelity recognition of self from nonself
and is a common and fundamental property in biological
systems. Self-sorting assembling process with discrimination
of subtle structural differences among similar isomers may lead
to largely different tertiary architectures of variable functions.
Structural diversity thus attained plays an important role in many
biological processes. In recent years, therefore, diverse efforts
have been made toward synthetic supramolecular systems that
achieve such high fidelity self-sorting assembling.1-5
process. Recently, we have explored three-dimensional porphy-
rin boxes that are formed via rigorous enantiomeric self-sorting
assembling of racemic 4-pyridine-appended meso-meso linked
Zn(II) diporphyrins, in which the structural matching of 90°
dihedral angle between the diporphyrin and the 4-pyridyl group
plays a key role toward the formation of box-shaped assemblies.8
In this case, it has been demonstrated that four molecules of
R-diporphyrin assemble into R-box and four molecules of
S-diporphyrin assemble into S-box via homochiral self-sorting
process. Mixed assembling would be expected to lead to
polymeric chains or ill-defined assemblies but such assemblies
Metalloporphyrins bearing a coordinating sidearm have been
used as an effective platform to build various supramolecular
structures with aids of multiple coordination interactions of
(4) (a) Cai, M.; Marlow, A. L.; Fettinger, J. C.; Fabris, D.; Haverlock, T. J.;
Moyer, B. A.; Davis, J. T. Angew. Chem. Int. Ed. 2000, 39, 1283-1285.
(b) Shi, X.; Fettinger, J. C.; Cai, M.; Davis, J. T. Angew. Chem., Int. Ed.
2000, 39, 3124-3127. (c) Cai, M.; Shi, X.; Sidorov, V.; Fabris, D.; Lam,
Y.; Davis, J. T. Tetrahedron 2002, 58, 661-671. (d) Shi, X.; Fettinger, J.
C.; Davis, J. T. J. Am. Chem. Soc. 2001, 123, 6738-6739.
(5) (a) Beijer, F. H.; Sijbesma, R. P.; Kooijman, H.; Spek, A. L.; Meijer, E.
W. J. Am. Chem. Soc. 1998, 120, 6761-6769. (b) Jolliffe, K. A.;
Timmerman, P.; Reinhoudt, D. N. Angew. Chem., Int. Ed. 1999, 38, 933-
937. (c) Castellano, R. K.; Nuckolls, C.; Rebek, J. Jr. J. Am. Chem. Soc.
1999, 121, 1, 11156-11163. (d) Shivanyuk, A.; Rebek, J. Jr. J. Am. Chem.
Soc. 2002, 124, 12074-12075. (e) Corbin, P. S.; Lawless, L. J.; Li, Z.;
Ma, Y.; Witmer, M. J.; Zimmerman, S. C. Proc. Natl. Acad. Sci. U.S.A.
2002, 99, 5099-5104. (f) Ma, Y.; Kolotuchin, S. V.; Zimmerman, S. C. J.
Am. Chem. Soc. 2002, 124, 13757-13769.
† Department of Chemistry, Graduate School of Science, Kyoto Uni-
versity, and CREST (Core Research for Evolutional Science and Technol-
ogy) of Japan Science and Technology Agency.
‡ Graduate School of Life Science, University of Hyogo, and RIKEN
Harima Institute/SPring-8.
§ Department of Chemistry, Graduate School of Science, Nagoya
University.
| Center for Ultrafast Optical Characteristics Control and Department of
Chemistry, Yonsei University.
(1) Stryer, L. Biochemistry, 4th ed.; W. H. Freeman: New York, 1995.
(2) (a) Lehn, J.-M. Science 2002, 295, 2400-2403. (b) Hollingsworth, M. D.
Science 2002, 295, 2410-2413. (c) Kra¨mer, R.; Lehn, J.-M.; Marquis-
Rigault, A. Proc. Natl. Acad. Sci. U.S.A. 1993, 90, 5394-5398.
(3) (a) Wu, A.; Chakraborty, A.; Fettinger, J. C.; Flowers II, R A.; Isaacs, L.
Angew. Chem., Int. Ed. 2002, 41, 4028-4031. (b) Wu, A.; Isaacs, L. J.
Am. Chem. Soc. 2003, 125, 4831-4835. (c) Mukhopadhyay, P.; Wu, A.;
Isaacs, L. J. Org. Chem. 2004, 69, 6157-6164.
(6) (a) Imamura, T.; Fukushima, K. Coord. Chem. ReV. 2000, 198, 133-156.
(b) Wojaczynski, J.; Latos-Grazynski, L. Coord. Chem. ReV. 2000, 204,
113-171. (c) Iengo, E.; Zangrando, E.; Alessio, E. Eur. J. Inorg. Chem.
2003, 2371-2384. (d) Satake, A.; Kobuke, Y. Tetrahedron 2005, 61, 13-
41, and references therein.
9
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J. AM. CHEM. SOC. 2006, 128, 7670-7678
10.1021/ja0611137 CCC: $33.50 © 2006 American Chemical Society

Assembling of meso-meso Linked Zn(II) Diporphyrins
A R T I C L E S
upfield shifts for the imide protons at 6.29 (Hc), 3.58 (Ha), and
2.65 (Hb) ppm, which indicates the coordination of the pyridyl
group to Zn(II) porphyrin (Figure 1b). On the other hand, the
1H NMR spectrum 2 in coordinating pyridine-d5 exhibits
corresponding peaks at normal chemical shifts; 9.69 (Ha), 9.36
(Hc), and 8.17 (Hb) ppm (Figure 1a). This observation indicates
that 2 exists as a monomeric porphyrin in pyridine. X-ray-quality
crystals of 2 were grown by vapor diffusion of acetonitrile into
its toluene solution. The crystal system is rhombohedral and
the cell volume is 27150(2) Å3. The crystal structure revealed
a triangular complex formed by complementary coordination
of the cinchomeronimide group to the Zn(II) atom with a
dihedral angle of 61° between the porphyrin mean planes (Figure
2).10 The pyridyl group is coordinated to the Zn center with an
angle of 88.8° and the Zn center is displaced 0.272 Å out of
the N4 plane that is slightly domed.
Next, meso-meso linked diporphyrin 7 bearing two cin-
chomeronimide groups at 10,10′-positions was prepared from
5,10-bis(3,5-di-tert-butylphenyl)porphyrin 3 as shown in Scheme
2. Porphyrin 3 was coupled with AgPF6 to give meso-meso
linked diporphyrin11 4 in 17% yield, which was nitrated with
AgNO2 in CHCl3 to afford 5 in 85% yield. Nitro groups of 5
were reduced with Pd-charcoal and NaBH4 to provide 10,10′-
diamino meso-meso linked Zn(II) diporphyrin 6 in 87% yield.
Final condensation of 6 with cinchomeronic anhydride was
performed in pyridine under reflux conditions for 12 h to furnish
10,10′-cinchomeronimide-appended meso-meso linked Zn(II)
diporphyrin 7. Importantly, a free rotation of the cinchomer-
onimide group is considerably restricted due to the steric
hindrance of the two imide-carbonyl groups, which gives rise
to three different stable atropisomers (in-in, in-out, and out-
out) with respect to the orientation of the nitrogen atom in the
pyridine moiety. This has been confirmed by detailed 1H NMR
examinations of separated conformational isomers of 7, as
explained in a later section. In addition, a free rotation around
the meso-meso linkage is severely prohibited,8,12 thus making
all the isomers to be chiral (R and S). Therefore, six isomers
Scheme 1
a Cinchomeronic anhydride, pyridine, reflux, 52%. Ar ) 3,5-di-tert-
butylphenyl.
were not observed. Complementary multiple coordination
interactions arising from meso-meso linked diporphyrin frame-
work help increase the association constants, such that the boxes
can be manipulated like covalently linked molecules. One
strategy to create assemblies of different shape may be to
displace the positions of coordinating nitrogen atoms from the
porphyrin plane. This idea drove us to examine self-sorting
assembling behaviors of meso-cinchomeronimide (3,4-pyridinedi-
carboximide)-substituted Zn(II) porphyrin 2 and 10,10′-cin-
chomeronimide-appended meso-meso linked Zn(II) diporphyrin
7. In noncoordinating solvents, the former undergoes complete
assembling to form its trimer (2)3, whereas the latter is shown
to exist as three stable conformers in respect of the orientation
of the pyridyl nitrogen atoms, which assemble differently to
construct trimeric (7)3, tetrameric (7)4, and pentameric rings (7)5,
respectively, through rigorous homochiral self-sorting processes.
Results and Discussion
Synthesis and Characterization. 10-Cinchomeronimide-
substituted 5,15-bis(3,5-di-tert-butylphenyl) Zn(II)-porphyrin 2
was prepared from condensation reaction of 5-amino-10,20-bis-
(3,5-di-tert-butylphenyl) Zn(II)-porphyrin9 1 with cinchomeronic
anhydride in 52% yield (Scheme 1). 1H NMR spectrum of 2 in
CDCl3 is very simple, featuring a simple set of peaks with large
(7) (a) Drain, C. M.; Lehn, J.-M. J. Chem. Soc. Chem. Commun. 1994, 2313-
2315. (b) Kobuke, Y.; Miyaji, H. J. Am. Chem. Soc. 1994, 116, 4111-
4112. (c) Hunter, C. A. Sarson, L. D. Angew. Chem., Int. Ed. Engl. 1994,
33, 2313-2316. (d) Wojaczynski, J.; Latos-Grazynski, L. Inorg. Chem.
1995, 34, 1044-1053. (e) Wojaczynski, J.; Latos-Grazynski, L.; Olmstead,
M. M.; Balch, A. L. Inorg. Chem. 1997, 36, 4548-4554. (f) Stibrany, R.
T.; Vasudevan, J.; Knapp, S.; Potenza, J. A.; Emge, T.; Schugar, H. J. J.
Am. Chem. Soc. 1996, 118, 3980-3981. (g) Stang, P. J.; Fan, J.; Olenyuk,
B. Chem. Commun. 1997, 1453-1454. (h) Slone, R. V.; Hupp, J. T. Inorg.
Chem. 1997, 36, 5422-5423. (i) Drain, C. M.; Nifiatis, F.; Vasenko, A.;
Batteas, J. D. Angew. Chem., Int. Ed. 1998, 37, 2344-2347. (j) Belanger,
S.; Hupp, J. T. Angew. Chem., Int. Ed. 1999, 38, 2222-2224. (k) Belanger,
S.; Hupp, J. T.; Stern, C. L.; Slone, R. V.; Watson, D. F.; Carrell, T. G. J.
Am. Chem. Soc. 1999, 121, 557-563. (l) Ogawa, K.; Kobuke, Y. Angew.
Chem., Int. Ed. 2000, 39, 4070-4073. (m) Fujita, N.; Biradha, K.; Fujita,
M.; Sakamoto, S.; Yamaguchi, K. Angew. Chem., Int. Ed. 2001, 40, 1718-
1721. (n) Merlau, M. L.; Mejia, M. del, P.; Nguyen, S.; Hupp, J. T. Angew.
Chem., Int. Ed. 2001, 40, 4239-4242. (o) Iengo, E.; Zangrando, E.; Minatel,
R.; Alessio, E. J. Am. Chem. Soc. 2002, 124, 1003-1013. (p) Mines, G.
A.; Tzeng, B.-C.; Stevenson, K. J.; Li, J.; Hupp, J. T. Angew. Chem., Int.
Ed. 2002, 41, 154-157. (q) Takahashi, R.; Kobuke, Y. J. Am. Chem. Soc.
2003, 125, 2372-2373. (r) Tsuda, A.; Sakamoto, S.; Yamaguchi, K.; Aida,
T. J. Am. Chem. Soc. 2003, 125, 15722-15723. (s) Suzuki, M.; Tsuge,
K.; Sasaki, Y.; Imamura, T. Chem. Lett. 2003, 32, 564-565. (t) Tominaga,
M.; Suzuki, K.; Kawano, M.; Kusukawa, T.; Ozeki, T.; Sakamoto, S.;
Yamaguchi, K.; Fujita, M. Angew. Chem., Int. Ed. 2004, 43, 5621-5625.
(u) Shoji, O.; Okada, S.; Satake, A.; Kobuke, Y. J. Am. Chem. Soc. 2005,
127, 2201-2210. (v) Tsuda, A.; Hu, H.; Tanaka, R.; Aida, T. Angew.
Chem., Int. Ed. 2005, 44, 4884-4888. (w) Prodi, A.; Chiorboli, C.;
Scandola, F.; Iengo, E.; Alessio, E.; Dobrawa, R.; Wu¨rthner, F. J. Am.
Chem. Soc. 2005, 127, 1454-1462.
are present in a solution of 7; R-7in-in, S-7in-in, R-7in-out, S-7in-out
,
R-7out-out, and S-7out-out (Scheme 3).
Structures of Aggregates. In noncoordinating solvents like
CDCl3, the 1H NMR spectrum of 7 displays distinct three
entities, featuring the protons of the pyridyl groups in the range
of 2.9-6.5 ppm as sharp peaks (Figure 3a). This observation
suggested that all the pyridyl groups in 7 are bound on Zn(II)
atoms of the other molecules of 7, probably forming three
different cyclic aggregates with complementary coordination.
Gel permeation chromatography (GPC) of this mixture revealed
distinct three fractions (I, II, and III) in a ratio of ca. 1:2:1 in
the order of increasing molecular weight. GPC analysis with
polystyrene standards indicated the molecular weights of the
fractions I, II, and III to be 4.8 × 103, 6.1 × 103, and 7.6 × 103
Da, which roughly correspond to trimeric, tetrameric, and
pentameric aggregates of 7, respectively. These three fractions
were actually separated by preparative GPC-HPLC in 17, 34,
and 16% isolated yields, respectively, on the basis of the amount
of 6 used.
(8) (a) Tsuda, A.; Nakamura, T.; Sakamoto, S.; Yamaguchi, K.; Osuka, A.
Angew. Chem., Int. Ed. 2002, 41, 2817-2821. (b) Hwang, I.-W.; Kamada,
T.; Ahn, T. K.; Ko, D. M.; Nakamura, T.; Tsuda, A.; Osuka, A.; Kim, D.
J. Am. Chem. Soc. 2004, 126, 16187-16198.
(9) Yoshida, N.; Ishizuka, T.; Youfu, K.; Murakami, M.; Miyasaka, H.; Okada,
T.; Nagata, Y.; Itaya, A.; Cho, H. S.; Kim, D.; Osuka, A. Chem. Eur. J.
2003, 9, 2854-2866.
(10) Crystal data for 2, (R-7in-in) and (R-7out-out)5: See Table 1 and SI.
3
(11) Nakamura, Y.; Hwang, I.-W.; Aratani, N.; Ahn, T. K.; Ko, D. M.; Takagi,
A.; Kawai, T.; Matsumoto, T.; Kim, D.; Osuka, A. J. Am. Chem. Soc. 2005,
127, 236-246.
(12) Yoshida, N.; Osuka, A. Tetrahedron Lett. 2000, 41, 9287-9291.
9
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A R T I C L E S
Kamada et al.
Figure 1. 1H NMR spectra of 2 (a) in pyridine-d5 and (b) in CDCl3. Arrows indicate the pyridyl protons.
ppm, and Hb at 2.95 ppm for the fraction III, respectively
(Figures 3b-d). It is important to note that only single sets of
the signals were observed for the fractions I and III, while two
1
sets of the signals were detected for the fraction II. H NMR
spectrum of as prepared 7 is a simple sum of those of the
fractions I, II, and III in a ratio of ca. 1:2:1, indicating that these
aggregates are stable in CDCl3 solution and there is no
scrambling of diporphyrin fragments. When these aggregates
1
were dissolved in pyridine-d5, their H NMR spectra became
very similar and exhibited the pyridyl protons without no
particular upfield shifts, indicating their dissociation. As dis-
cussed in a later section, the dissociation of 7 in pyridine has
been supported also by the absorption spectra and CD spectra.
The 1H NMR spectra of the fractions I, II, and III were similar
but were distinctly different from one another, particularly in
the chemical shifts of the protons due to the inner â-protons
near the imide group (Supporting Information; SI), which has
been interpreted to indicate that the three aggregates consist of
respective different diporphyrin conformers. Most probably, the
Figure 2. X-ray crystal structure of (2)3. Solvent molecules, hydrogen
atoms, and meso-aryl groups are omitted for clarity.
Scheme 2
three conformers can be assigned as 7in-in, 7in-out, and 7out-out
,
(Scheme 3). These isomers are conformationally rather stable,
as shown by heating experiments (110 °C, 24 h, in pyridine) of
these separated conformers that led to only ca. 10% isomer-
ization.
Despite many attempts to determine the molecular weights
of the fractions I, II, and III, their parent ion peaks as aggregates
could not be detected either by MALDI-TOF, FAB, or cold-
spray ionization mass techniques. Thus, we attempted X-ray
diffraction analysis of these aggregates. In the course of these
attempts, we found that chiral separation of the fraction I was
possible through a chiral HPLC column (SI) and reasonably
nice crystals of the fraction I were obtained by slow diffusion
of acetonitrile into a toluene solution of the chiral fraction I.
X-ray diffraction analysis on this crystal provided preliminary
a AgPF6, CHCl3, 17%, bAgNO2, I2, CHCl3, 85%. cNaBH4, Pd/C, CH2Cl2,
MeOH, 87%. dCinchomeronic anhydride, pyridine, reflux, 67%. Ar ) 3,5-
di-tert-butylphenyl.
1H NMR spectra of the fractions I, II, and III are different
from one another, exhibiting the pyridyl protons; Hc at 6.49
ppm, Ha at 4.03 ppm, and Hb at 2.94 ppm for the fraction I, Hc
at 6.52 and 6.16 ppm, Ha at 3.82 and 3.15 ppm, Hb at 3.29 and
3.15 ppm for the fraction II, and Hc at 6.15 ppm, Ha at 3.90
9
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Assembling of meso-meso Linked Zn(II) Diporphyrins
A R T I C L E S
Scheme 3. Schematic Representation of Self-Sorting Process of Diporphyrins
data, which indicated a pair of trimers in the unit cell. Each
trimer was constructed by complementary coordination of three
molecules of an in-in conformer (R-7in-in) (SI). Largely due to
the disorder of many solvent molecules contained in the crystal,
the X-ray data remain preliminary level but the main skeletal
structure should be certain. As more convincing information,
we have succeeded in X-ray crystal diffraction analysis of the
fraction III. After many attempts, X-ray-quality crystals were
is monoclinic and the cell volume is quite large, 46060(8) Å3.
The crystal structure thus determined shows a symmetric
pentameric aggregate consisting of five molecules of R-7out-out
(Figure 4). The aggregate (R-7out-out)5 exhibits a C5 symmetric
pentagonal cylindrical structure with sides of ca. 11.5 Å and
internal angles of ca. 108°. In the crystal, the aggregates (R-
7out-out)5 are stacked in a tubular manner to form an infinite
channel of ca. 10 Å diameter (Figure 5). Each pentagonal
channel unit contacts through CH-π interactions between 3,5-
di-tert-butylphenyl groups and Zn(II) porphyrin planes to form
a linear zigzag network (Figure 5c). Then, the fraction II has
been rationally assigned as a tetrameric aggregate (7)4 composed
of four molecules of an in-out conformer (R-7in-out) on the
basis of its GPC retention time that indicated its molecular size
obtained by slow diffusion of acetonitrile into a toluene solution
13
of optically pure R-7out-out
.
X-ray diffraction data set for (R-
7
out-out)5 was collected with 44571 unique reflections (>2σ(I))
at BL44B2 beamline of SPring-8 Japan.10 The crystal system
(13) Diporphyrin 4 was separated into R-4 and S-4, and R-4 was converted to
R-7 via the same synthetic route.
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A R T I C L E S
Kamada et al.
Figure 3. 1H NMR spectra of as prepared 7 (a), and of the fractions III, II, and I, ((b), (c), and (d)) in CDCl3. The fractions III, II, and I have been assigned
as (7out-out)5, (7in-out)4, and (7in-in)3, respectively. See the discussion in the text.
to be larger than (7)3 and smaller than (7)5. Cyclic symmetric
structures of (7)3 and (7)5 well explain their H NMR data
atoms are coordinated to the Zn(II) atoms with angles of N-Zn
and porphyrin 24 core atoms plane 88 and 85° for (R-7′in-in 3
1
)
showing single sets of signals due to the pyridyl protons, since
all the constitutional diporphyrins are identical. On the other
hand, the observed two sets of signals due to the pyridyl protons
and (R-7′out-out)5 respectively. On the other hand, a quadratic
prismatic structure was calculated for (R-7′in-out)4, in which four
molecules of 7′in-out assembled by an alternate in- and out-
pyridyl coordination with angles of N-Zn and porphyrin 24
core atoms plane, 89 and 86° for inward- and outward-oriented
cinchomeronimides. The calculated structure of (R-7′in-out)4 well
explains the 1H NMR spectrum, since all the inward- and
outward-orientating pyridyl groups are respectively identical in
the aggregate.
1
in a 1:1 ratio in the H NMR of (7)4 can be explained by the
presence of the inward and outward orientating pyridyl protons.
Energy minimized structures of (R-7′in-in)3, (R-7′in-out)4, and
(R-7′out-out)5 were calculated by the DFT method in which meso
3,5-di-tert-butylphenyl substituents of 7 are replaced by hydro-
gen (Figure 6). Calculated structures for (R-7′in-in)3 and (R-
7′out-out 5
)
were almost exactly the same as those of the
UV-Vis Absorption Spectra. Figure 7 shows the absorption
spectra of (R-7in-in)3, (R-7in-out)4, and (R-7out-out)5 in pyridine
corresponding X-ray structures, in which the pyridyl nitrogen
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Assembling of meso-meso Linked Zn(II) Diporphyrins
A R T I C L E S
Figure 4. X-ray crystal structure of (R-7out-out)5; top view (left) and side
view (right). Solvent molecules, hydrogen atoms, and meso-aryl groups are
omitted for clarity.
Figure 6. DFT calculated structures of (a) (R-7′in-in)3, (b) (R-7′in-out)4,
and (c) (R-7′out-out)5.
Figure 5. van der Waals structure (top, left) and packing diagram for (R-
(7out-out)5 that are formed via homochiral self-sorting of respec-
tive R- or S-enantiomer of 7in-in, 7in-out, and 7out-out should be
7out-out)5; perspective view (top, right) and top view (bottom). Solvent
molecules and hydrogen atoms on tert-butyl groups are omitted for clarity.
all chiral. Among these aggregates, (7in-in)3 was actually
separated into (R-7in-in)3 and (S-7in-in)3 through a chiral HPLC
column. In an alternate route, the optically pure aggregates (R-
(a) and in CHCl3 (b). It has been known that the exciton coupling
in the Soret band of meso-meso linked diporphyrins is sensitive
to the dihedral angle between the porphyrins.14 The absorption
spectra in pyridine are practically the same for the three samples,
exhibiting split Soret bands due to the exciton coupling between
the porphyrin units.15 The observed splitting widths are all ca.
1960 cm-1, which are typical for free meso-meso linked zinc-
(II) diporphyrins having wide distribution of dihedral angle
between the two porphyrins. On the other hand, the absorption
spectra of (R-7in-in)3, (R-7in-out)4, and (R-7out-out)5 in CHCl3 are
different from one another, which is caused by different exciton
coupling in each aggregate (Figure 7b). The observed narrow
splitting widths in the spectra in CHCl3 (1540, 1390, and 1290
cm-1 for (R-7in-in)3, (R-7in-out)4, and (R-7out-out)5, respectively)
has been interpreted in terms of considerably reduced confor-
mational freedom of the diporphyrin segments in the ag-
gregates.8
7in-in)3, (R-7in-out)4, and (R-7out-out)5, and (S-7in-in)3, (S-7in-out)4,
and (S-7out-out)5 were constructed from preseparated optically
pure diporphyrins R-7 and S-7, respectively, and were separated
by preparative GPC-HPLC. Three sets of (R-7in-in)3 and (S-
7
in-in)3, (R-7in-out)4 and (S-7in-out)4, and (R-7out-out)5 and (S-
7out-out)5 are identical to their respective racemic mixtures in
terms of the 1H NMR and absorption spectra, while the circular
dichroism (CD) spectra in CHCl3 exhibit different strong Cotton
effects depending on the ring size (3, 4, and 5) respectively
and are perfect mirror images to each other (Figure 8 and SI).
In pyridine, the optically pure aggregates (7in-in)3, (7in-out)4, and
(7out-out)5 are all completely dissociated, as seen from their weak
and reverse Cotton effects compared with those in CHCl3.
The association constants of (7in-in)3 and (7out-out)5 have been
estimated to be both very large, > 1018 M-2 and > 1027 M-4
,
respectively, irrespective of racemic or optically pure precursors
on the basis of concentration independence of their absorption
spectra up to rather high dilution (∼10-7 M). This can be
explained by highly complementary and multipoint interactions
without significant strain. On the other hand, the association
behavior of 7in-out depends on precursor, either optically pure
or racemic. The association constant of optically pure R-7in-out
Chiral Separation, CD Spectra, and Association Con-
stants. Since conformational isomers of 7 (7in-in, 7in-out, and
7
out-out) are all chiral, the aggregates (7in-in)3, (7in-out)4, and
(14) (a) Yoshida, N.; Ishizuka, T.; Osuka, A.; Jeong, D. H.; Cho, H. S.; Kim,
D.; Matsuzaki, Y.; Nogami, A.; Tanaka, K. Chem. Eur. J. 2003, 9, 58-
75. (b) Jeong, D. H.; Jang, S. M.; Hwang, I.-W.; Kim, D.; Yoshida, N.;
Osuka, A. J. Phys. Chem. A 2002, 106, 11054-11063.
(15) (a) Aratani, N.; Osuka, A.; Kim, Y. H.; Jeong, D. H.; Kim, D. Angew.
Chem., Int. Ed. 2000, 39, 1458-1462. (b) Aratani, N.; Takagi, A.;
Yanagawa, Y.; Matsumoto, T.; Kawai, T.; Yoon, Z. S.; Kim, D.; Osuka,
A. Chem. Eur. J. 2005, 11, 3389-3404.
was estimated to be certainly large as much as 2.0 × 1016 M-3
,
but the UV-vis titration curve for the association of racemic
7in-out was complicated, which precluded precise estimation of
9
J. AM. CHEM. SOC. VOL. 128, NO. 23, 2006 7675

A R T I C L E S
Kamada et al.
Figure 7. UV-vis absorption spectra of (R-7out-out)5, (R-7int-out)4 and (R-7in-in)3 in pyridine (a) and in CHCl3 (b).
Figure 8. CD spectra of R-7 (a) in CHCl3 and (b) in pyridine.
Experimental Section
the association constant. These results indicate weaker comple-
mentary coordination interaction and hence imperfect enantio-
All reagents and solvents were of the commercial reagent grade and
were used without further purification except where noted. Dry CHCl3
were obtained by distilling over CaH2. Spectroscopic grade CHCl3 and
meric self-sorting for 7in-out
.
Summary. We have demonstrated that the meso-cinchom-
eronimide appended Zn(II) porphyrin 2 forms a cyclic trimer,
while the diporphyrins 7 exhibit high-fidelity self-sorting
assembling to form discrete cyclic trimer, tetramer, and pentamer
1
pyridine were used as solvents for all spectroscopic studies. H NMR
spectra were recorded on a JEOL ECA-delta-600 spectrometer, and
chemical shifts were reported as the delta scale in ppm relative to CHCl3
(δ ) 7.260 ppm) or pyridine (δ ) 8.71 ppm). UV-vis absorption
spectra were recorded on a Shimadzu UV-3100 spectrometer. Mass
spectra were recorded on a JEOL HX-110 spectrometer, using positive-
FAB ionization method with accelerating voltage 10 kV and a
3-nitrobenzyl alcohol matrix, and on a Shimadzu KRATOS KOMPACT
MALDI 4 spectrometer, using positive-MALDI ionization method with/
without 9-nitroanthracene (9NA) matrix. All theoretical calculations
were carried out using the Gaussian 03 program.16 Initial structures of
aggregates, where meso-aryl groups were omitted and replaced with
hydrogen atoms, were obtained through optimization with the AM1
Hamiltonian. All structures were then optimized with Becke’s three-
parameter hybrid exchange functional and the Lee-Yang-Parr cor-
relation functional (B3LYP), employing the LANL2DZ basis set for
zinc atom, and 3-21G* basis set for the other atom.
with large association constants from 7in-in, 7in-out, and 7out-out
,
respectively, through almost perfect discrimination of enantio-
meric and conformational differences of the meso-cinchomer-
onimide substituents. In the latter self-sorting processes, the
dihedral angles dictated by the two pyridyl nitrogen atoms
control the size of the aggregates; the trimer from 7in-in, the
tetarmer from 7in-out, and the pentamer from 7out-out. Exclusive
formation of the discrete cyclic aggregates without no ap-
preciable amount of polymeric aggregate is also notable, which
is probably driven by favorable entropic factors for the formation
of cyclic aggregates. As such, meso-meso linked diporphyrins
are interesting and unique structural platforms that provide large
discrete cyclic constructs via unique self-sorting assembling
process. Exploration of even larger discrete porphyrin rings with
appropriate optical functions will be the subject of further
investigation.
Zn(II) 10-Cinchomeronimide-5,15-bis(3,5-di-tert-butylphenyl)-
porphyrin 2. A solution of Zn(II) 5-amino-10,20-bis(3,5-di-tert-
butylphenyl)porphyrin 1 (40 mg, 0.054 mmol) and cinchomeronic
anhydride (80 mg, 0.54 mmol) in pyridine (20 mL) was heated under
9
7676 J. AM. CHEM. SOC. VOL. 128, NO. 23, 2006

Assembling of meso-meso Linked Zn(II) Diporphyrins
A R T I C L E S
reflux for 14 h. After removal of the solvent, the residue was separated
Ar), 1.53 (s, 18H, t-Bu), 1.44 (s, 9H, t-Bu), and 1.43 ppm (s, 9H, t-Bu);
UV-vis (pyridine) λmax ) 440, 462, and 683 nm; MALDI-TOF-MS
m/z ) 1527.9, calcd. for C96H104N10Zn2 m/z ) 1528.7.
over a silica gel column with a mixture of THF and hexane to give 2
1
(25 mg, 0.028 mmol, 52%); H NMR (CDCl3) δ 10.37 (s, 1H, Por-
meso), 9.42 (d, J ) 5 Hz, 2H, Por-â), 9.09 (d, J ) 5 Hz, 2H, Por-â),
8.73 (br, 2H, Por-â), 8.25 (br, 2H, Por-â), 8.08 (s, 2H, Ar), 7.85 (s,
2H, Ar), 7.78 (s, 2H, Ar), 6.29 (br, 1H, Py), 3.58 (br, 1H, Py), 2.65
(br, 1H, Py), 1.63 (s, 18H, t-Bu), and 1.46 ppm (s, 18H, t-Bu); UV-
vis (CHCl3) λmax ) 420 and 548 nm; FAB-MS m/z ) 894.35, calcd.
for C55H54N6O2Zn m/z ) 894.36.
10,10′-Bis(cinchomeronimide)-Appended meso-meso Linked Zn-
(II) Diporphyrin 7 and its Separation to (7out-out)5, (7in-out
) and
4
(7in-in)3. A solution of 6 (45 mg, 0.029 mmol) and cinchomeronic
anhydride (132 mg, 0.883 mmol) in pyridine (20 mL) was heated under
reflux for 12 h. After the removal of the solvent, the residue was purified
over a silica gel column with THF/hexane. The solvent was removed
by a rotary evaporator and the residue was separated by a size exclusion
column chromatography with CHCl3 as an eluent to give (7out-out)5 (8.5
mg, 16%), (7in-out)4 (18.1 mg, 34%) and (7in-in)3 (9.1 mg, 17%).
Meso-meso Linked Zn(II) Diporphyrin 4. A stock solution of
AgPF6 in dry CH3CN (0.12 M, 1.85 mL) was added to a solution of
Zn(II) 5,10-bis(3,5-di-tert-butylphenyl) porphyrin 3 (300 mg, 0.400
mmol) in dry CHCl3 (270 mL), and the resulting mixture was stirred
for 1 h at 5 °C in the dark. The reaction was stopped by washing with
water and the organic layer was dried over anhydrous Na2SO4. The
solvent was removed by a rotary evaporator and the residue was
separated by a preparative size exclusion column with CHCl3 as an
eluent. Zn(II) diporphyrin 4 was obtained after recrystallization from
CH2Cl2/hexane (53 mg, 17%); 1H NMR (CDCl3) δ 10.33 (s, 2H, Por-
meso), 9.48 (d, J ) 5 Hz, 2H, Por-â), 9.24 (d, J ) 4 Hz, 2H, Por-â),
9.15 (d, J ) 5 Hz, 2H, Por-â), 9.15 (d, J ) 5 Hz, 2H, Por-â), 9.08 (d,
J ) 5 Hz, 2H, Por-â), 8.73 (d, J ) 5 Hz, 2H, Por-â), 8.29 (d, J ) 5
Hz, 2H, Por-â), 8.22 (s, 2H, Ar-H), 8.20 (s, 2H, Ar-H), 8.14 (d, J )
5 Hz, 2H, Por-â), 8.10 (s, 2H, Ar-H), 8.09 (s, 2H, Ar-H), 7.87 (s,
2H, Ar-H), 7.69 (s, 2H, Ar-H), 1.61 (s, 18H, t-Bu), 1.60 (s, 18H,
t-Bu), 1.44 (s, 18H, t-Bu), and 1.43 ppm (s, 18H, t-Bu); UV-vis
(CHCl3) λmax ) 412, 450, and 552 nm; MALDI-TOF-MS m/z )
1498.8, calcd. for C96H102N8Zn2 m/z ) 1498.7.
1
(7out-out)5. H NMR (CDCl3) δ 8.98 (d, J ) 4 Hz, 2H, Por-â), 8.96
(d, J ) 4 Hz, 2H, Por-â), 8.76 (d, J ) 4 Hz, 2H, Por-â), 8.56 (d, J )
5 Hz, 2H, Por-â), 8.28 (d, J ) 5 Hz, 2H, Por-â), 8.22 (br, 2H, Ar), 8.2
(br, 2H, Ar), 7.98 (br, 2H, Ar), 7.9 (d, J ) 4 Hz, 2H, Por-â), 7.85 (d,
J ) 4 Hz, 2H, Por-â), 7.79 (br, 2H, Ar), 7.77 (br, 2H, Ar), 7.63 (t, J
) 2 Hz, 2H, Ar), 7.08 (d, J ) 4 Hz, 2H, Por-â), 6.15 (d, J ) 6 Hz,
2H, Py), 3.90 (s, 2H, Py), 2.95 (d, J ) 6 Hz, 2H, Py), 1.61 (s, 18H,
t-Bu), 1.46 (s, 18H, t-Bu), 1.35 (s, 18H, t-Bu), and 1.31 ppm (s, 18H,
t-Bu); 1H NMR (pyridine-d5) δ 9.80 (d, J ) 4 Hz, 2H, Por-â), 9.57 (s,
2H, Py), 9.45 (d, J ) 4 Hz, 2H, Por-â), 9.43 (d, J ) 4 Hz, 2H, Por-â),
9.33 (m, 4H, Por-â + Py), 9.20 (d, J ) 5 Hz, 2H, Por-â), 8.97 (d, J )
4 Hz, 2H, Por-â), 8.53 (br, 2H, Ar), 8.51 (br, 2H, Ar), 8.50 (br, 2H,
Ar), 8.48 (br, 2H, Ar), 8.19 (d, J ) 4 Hz, 2H, Por-â), 8.07 (d, J ) 4
Hz, 2H, Por-â), 8.06 (br, 2H, Ar), 8.03 (d, J ) 6 Hz, 2H, Py), 7.98 (t,
J ) 2 Hz, 2H, Ar), 1.56 (s, 18H, t-Bu), 1.55 (s, 18H, t-Bu), 1.48 (s,
18H, t-Bu), and 1.47 ppm (s, 18H, t-Bu); UV-vis (CHCl3) λmax
)
428, 453, and 571 nm.
10,10′-Dinitrated meso-meso Linked Zn(II) Diporphyrin 5. A
solution of AgNO2 (60 mg, 0.39 mmol) in dry CH3CN (2.0 mL) was
added to a solution of 4 (147 mg, 0.098 mmol) and iodine (100 mg,
0.39 mmol) in CHCl3 (30 mL). After refluxing for 10 min, the reaction
mixture was washed with water, aqueous Na2S2O4, water and brine,
and was dried over anhydrous Na2SO4. The solvent was removed by a
rotary evaporator and the residue was separated by silica gel column
chromatography with a mixture of CH2Cl2 and hexane. A solution of
Zn(OAc)2 in the methanol was added to a solution of the separated
compound in CH2Cl2. After stirring for 1 h, the solution was washed
with water and dried over anhydrous Na2SO4. The solvent was removed
1
(7in-out)4. H NMR (CDCl3) δ 9.00 (s, 2H, Por-â), 8.99 (d, J ) 5
Hz, 1H, Por-â), 8.95 (d, J ) 5 Hz, 1H, Por-â), 8.85 (d, J ) 5 Hz, 1H,
Por-â), 8.71 (d, J ) 4 Hz, 1H, Por-â), 8.58 (d, J ) 4 Hz, 1H, Por-â),
8.49 (d, J ) 5 Hz, 2H, Por-â), 8.23 (d, J ) 4 Hz, 1H, Por-â), 8.21 (br,
1H, Ar), 8.11 (br, 1H, Ar), 8.06 (br, 1H, Ar), 8.03 (br, 1H, Ar), 8.00
(br, 1H, Ar), 7.97 (br, 1H, Ar), 7.96 (d, J ) 4 Hz, 1H, Por-â), 7.94 (d,
J ) 4 Hz, 1H, Por-â), 7.89 (br, 1H, Ar), 7.83 (br, 1H, Ar), 7.69 (d, J
) 4 Hz, 1H, Por-â), 7.65 (t, J ) 2 Hz, 1H, Ar), 7.59 (d, J ) 5 Hz, 1H,
Por-â), 7.55 (t, J ) 2 Hz, 1H, Ar), 7.31 (d, J ) 4 Hz, 1H, Por-â), 6.72
(d, J ) 5 Hz, 1H, Por-â), 6.52 (d, J ) 6 Hz, 1H, Py), 6.16 (d, J ) 6
Hz, 1H, Py), 3.82 (s, 1H, Py), 3.52 (s, 1H, Py), 3.29 (d, J ) 6 Hz, 1H,
Py), 3.15 (d, J ) 6 Hz, 1H, Py), 1.62 (s, 9H, t-Bu), 1.58 (s, 9H, t-Bu),
1.49 (s, 9H, t-Bu), 1.46 (s, 9H, t-Bu), 1.39 (s, 27H, t-Bu), and 1.09
1
by a rotary evaporator to give 5 (132 mg, 85%); H NMR (CDCl3) δ
9.24 (br, 2H, Por-â), 9.14 (d, J ) 5 Hz, 2H, Por-â), 9.04 (d, J ) 5 Hz,
2H, Por-â), 9.02 (d, J ) 5 Hz, 2H, Por-â), 8.92 (br, 2H, Por-â), 8.67
(d, J ) 5 Hz, 2H, Por-â), 8.24 (d, J ) 5 Hz, 2H, Por-â), 8.19 (br, 2H,
Ar), 8.11 (br, 2H, Ar), 8.07 (br, 2H, Ar), 8.02 (br, 2H, Ar), 7.97 (d, J
) 5 Hz, 2H, Por-â), 7.89 (t, J ) 2 Hz, 2H, Ar), 7.71 (t, J ) 2 Hz, 2H,
Ar), 1.62 (s, 18H, t-Bu), 1.59 (s, 18H, t-Bu), 1.47 (s, 18H, t-Bu), and
1.43 ppm (s, 18H, t-Bu); UV-vis (CHCl3) λmax ) 412, 450, and 552
nm; MALDI-TOF-MS m/z ) 1588.5, calcd. for C96H100N10O4Zn2 m/z
) 1588.7.
1
ppm (s, 9H, t-Bu); H NMR (pyridine-d5) δ 9.80 (d, J ) 4 Hz, 2H,
Por-â), 9.57 (s, 2H, Py), 9.45 (d, J ) 4 Hz, 2H, Por-â), 9.43 (d, J )
4 Hz, 2H, Por-â), 9.34 (m, 4H, Por-â + Py), 9.20 (d, J ) 5 Hz, 1H,
Por-â), 9.20 (d, J ) 5 Hz, 1H, Por-â), 8.98 (d, J ) 4 Hz, 1H, Por-â),
8.97 (d, J ) 4 Hz, 1H, Por-â), 8.53 (br, 2H, Ar), 8.51 (br, 4H, Ar),
8.48 (br, 1H, Ar), 8.47 (br, 1H, Ar), 8.21 (d, J ) 4 Hz, 1H, Por-â),
8.18 (d, J ) 4 Hz, 1H, Por-â), 8.08 (d, J ) 4 Hz, 1H, Por-â), 8.06 (br,
2H, Ar), 8.03 (d, J ) 4 Hz, 1H, Por-â), 8.03 (d, J ) 6 Hz, 1H, Py),
8.02 (d, J ) 6 Hz, 1H, Py), 7.98 (t, J ) 2 Hz, 2H, Ar), 1.56 (s, 18H,
t-Bu), 1.55 (s, 18H, t-Bu), 1.49 (s, 18H, t-Bu), 1.48 (s, 9H, t-Bu), and
1.47 ppm (s, 9H, t-Bu); UV-vis (CHCl3) λmax ) 427, 454, and 569
nm.
(7in-in)3. 1H NMR (CDCl3) δ 9.01 (s, 4H, Por-â), 8.87 (d, J ) 5 Hz,
2H, Por-â), 8.70 (d, J ) 5 Hz, 2H, Por-â), 8.42 (d, J ) 5 Hz, 2H,
Por-â), 8.26 (br, 2H, Ar), 8.21 (br-s, 2H, Ar), 7.99 (d, J ) 5 Hz, 2H,
Por-â), 7.92 (br, 2H, Ar), 7.91 (br, 2H, Ar), 7.82 (br, 2H, Ar), 7.80 (d,
J ) 5 Hz, 2H, Por-â), 7.69 (t, J ) 2 Hz, 2H, Ar), 6.79 (d, J ) 5 Hz,
2H, Por-â), 6.48 (d, J ) 6 Hz, 2H, Py), 4.03 (s, 2H, Py), 2.94 (d, J )
6 Hz, 2H, Py), 1.68 (s, 18H, t-Bu), 1.49 (s, 18H, t-Bu), 1.48 (s, 18H,
10,10′-Diaminated meso-meso Linked Zn(II) Diporphyrin 6.
Diporphyrin 5 (75 mg, 0.047 mmol) was dissolved in CH2Cl2 (30 mL)
and methanol (30 mL), to which 10% Pd/carbon (50 mg) was added.
Then, NaBH4 (36 mg, 0.94 mmol) was added to the solution, and the
resulting reaction mixture was stirred for 20 min at room temperature.
Pd/carbon was filtered off and the filtrate was washed with water and
the organic layer was dried over anhydrous Na2SO4. The solvent was
removed by a rotary evaporator and the residue was separated by silica
1
gel chromatography with CH2Cl2 to give 6 (63 mg, 87%); H NMR
(pyridine-d5) δ 9.89 (d, J ) 4 Hz, 2H, Por-â), 9.51 (d, J ) 5 Hz, 2H,
Por-â), 9.04 (br, 4H, NH2), 8.92 (m, 4H, Por-â), 8.11 (d, J ) 5 Hz,
2H, Por-â), 8.59 (d, J ) 5 Hz, 2H, Por-â), 8.39 (s, 2H, Ar), 8.36 (s,
2H, Ar), 8.33 (s, 2H, Ar), 8.29 (s, 2H, Ar), 8.23 (d, J ) 5 Hz, 2H,
Por-â), 8.05 (d, J ) 4 Hz, 2H, Por-â), 8.00 (s, 2H, Ar), 7.84 (s, 2H,
1
t-Bu), and 1.38 ppm (s, 18H, t-Bu); H NMR (pyridine-d5) δ 9.80 (d,
J ) 4 Hz, 2H, Por-â), 9.57 (s, 2H, Py), 9.45 (d, J ) 4 Hz, 2H, Por-â),
9.43 (d, J ) 4 Hz, 2H, Por-â), 9.34 (m, 4H, Por-â + Py), 9.21 (d, J )
5 Hz, 2H, Por-â), 8.98 (d, J ) 4 Hz, 2H, Por-â), 8.53 (br, 2H, Ar),
8.51 (br, 4H, Ar), 8.48 (br, 2H, Ar), 8.21 (d, J ) 4 Hz, 2H, Por-â),
(16) Frisch, M. J.; et al. Gaussian03, Revision B.05. Gaussian, Inc.: Pittsburgh,
PA, 2003.
9
J. AM. CHEM. SOC. VOL. 128, NO. 23, 2006 7677

A R T I C L E S
Kamada et al.
Table 1. Crystal Data and Structure Refinement for (2)3 and (R-7out-out
)
5
(2)3
(R-7out out)5.
-
formula
formula weight
temp
wavelength
crystal system
space group
unit cell dimensions
C376H324N47O17Zn6
6149.04
C522 H722 N60 O20 Zn10
8811.30
120(2) K
293(2) K
0.71073 Å
Rhombohedral
R-3
0.71073 Å
Monoclinic
P21
a ) 22.8553(7) Å
b ) 22.8553(7) Å
c ) 60.016(4) Å
27150(2) Å3
R ) 90°
â ) 90°
γ ) 120°
a ) 29.95(3) Å
b ) 54.46(5) Å
c ) 30.26(3) Å
46060(8) Å3
2
R ) 90°
â ) 111.06(5)°
γ ) 90°
vol
Z
3
density (calculated)
absorption coeff
F(000)
crystal size
theta range for data collection
reflections collected
independent reflections
absorption correction
refinement method
data/restraints/parameters
goodness-of-fit on F2
final R indices [I>2sigma(I)]
R indices (all data)
CCDC reference no.
1.128 Mg/m3
0.454 mm-1
0.635 Mg/m3
0.290 mm-1
9468
9651
0.40 × 0.30 × 0.10 mm3
1.08 to 28.32°
52174
0.20 × 0.20 × 0.20 mm3
1.72 to 18.41°
56692
13839 [R(int) ) 0.0953]
44571 [R(int) ) 0.3143]
Empirical
Empirical
Full-matrix least-squares on F2
13839/15/646
0.969
56692/6191/4246
2.415
R1 ) 0.1147, wR2 ) 0.3123
R1 ) 0.1277, wR2 ) 0.3186
281544
R1 ) 0.0992, wR2 ) 0.2875
R1 ) 0.2003, wR2 ) 0.3300
281543
8.06 (br, 2H, Ar), 8.05 (d, J ) 4 Hz, 2H, Por-â), 8.03 (d, J ) 6 Hz,
2H, Py), 7.98 (t, J ) 2 Hz, 2H, Ar), 1.56 (s, 18H, t-Bu), 1.55 (s, 18H,
t-Bu), 1.49 (s, 18H, t-Bu), and 1.47 ppm (s, 18H, t-Bu); UV-vis
(CHCl3) λmax ) 426, 456, and 571 nm.
These aggregates have been examined by MALDI-TOF mass
spectroscopy, which all showed peaks at the corresponding diporphyrin
unit m/z ) 1786.8 (calcd. for C110H106N12O4Zn2 m/z ) 1790.9) without
no parent ion peaks of the aggregates.
X-ray Diffraction Analysis. Data collection for the compounds (2)3
was carried out at -153 °C on a Bruker SMART APEX with graphite
monochromated MoKR radiation (λ ) 0.710 69 Å). Details of the
crystallographic data are listed in Table 1. The structure was solved
by direct methods (SHELXS-97)17 and refined with full-matrix least-
squares technique (SHLEXL-97).
pentagonal mainframes from the peaks that the program indicated. The
mainframes of the R-7out-out structure were built based on the Zn sites
with the program XFIT,19 followed by refinement with SHELXL-97.
Models for side chains were fitted to electron density map with
coefficient of Fo-Fc. Some residual peaks in the solvent area were found
in the electron density map, but none of them could be fitted as a solvent
molecule. Because of the paucity of data, geometrical restraints were
applied to chemically equivalent bonds and to make the phenyl and
pyridyl groups planar. wR2 ) 0.319, R1 ) 0.115 [for 44571 refractions
with F2 > 2σ(F2)], goodness of fit on F2 ) 2.42 on 4246 parameters.
The absolute structure was determined to be R on the basis of anomalous
dispersion (Flack parameter20 0.225(13).
The structure of (R-7in-in
) was solved and refined with similar
3
procedure to that of (R-7out-out)5. Eight toluene molecules and nine
acetonitrile molecules could be assigned. wR2 ) 0.438, R1 ) 0.188
[for 12490 refractions with F2 > 2σ(F2)], goodness of fit on F2 ) 1.97
on 6950 parameters. The absolute structure was determined to be R on
the basis of anomalous dispersion (Flack parameter20 0.04(4).
CCDC-281543 ((2)3), CCDC-281545 ((R-7in-in)3), and CCDC-
281544 ((R-7out-out)5) contain the supplementary crystallographic data,
which can be obtained free of charge from the Cambridge Crystal-
lographic Data Centre via www.ccdc.cam.ac. uk/data_request.cif.
The X-ray diffraction data set (R-7out-out
) were collected at the
5
BL44B2 beamline, SPring-8, Japan. Since the crystals of (R-7)5 were
very fragile and rapidly lost solvent in air, they were kept in mother
liquor throughout handling and data collection. A Lindemann tube (0.5
mm) was used for sealing crystal, which was injected with high vacuum
silicon grease (Dow corning) up to approximately 1 cm from the bottom
of the tube and then filled with the mother liquor. Crystal was
transferred into the tube, and let it sink until it touched the grease layer.
To fix the crystal, it was then carefully pushed down with a thin glass
capillary toward the grease layer so that it was partially buried in the
layer. During data collection, neither crystal slippage nor damage of
crystal was detected. The wavelength of the incident beam and sample-
detector distance were set at 0.6000 Å and 140 mm, respectively. A
total of 360 images with 1° oscillation were recorded using the ADSC
Quantum 210 CCD detector system, which were processed and scaled
using the program HKL2000 package18 The structure was solved by
the direct method with SHELXS-97. We could easily recognize the
Acknowledgment. The work was partly supported by Grant-
in-Aid from the Ministry of Education, Culture, Sports, Science
and Technology, Japan and 21st Century COE on Kyoto
University Alliance for Chemistry (A.O.) and the National
Creative Research Initiatives Program of the Ministry of Science
and Technology of Korea (D.K.). We thank Prof. H. Tamiaki
at Ritsumeikan University for CD measurements.
Supporting Information Available: GPC-HPLC chromato-
gram, chiral HPLC chromatogram, spectral data including CD,
1H NMR in pyridine-d5, X-ray analysis data and structures, and
DFE calculated structures. This material is available free of
charge via the Internet at http://pubs.acs.org.
(17) Sheldrick, G. M. SHELXS-97 and SHELXL-97, Program for the Solution
and Refinement of Crystal Structures, University of Go¨ttingen, Go¨ttingen,
Germany, 1997.
(18) Otwinowski, Z.; Minor, W. Methods Enzymol. 1997, 276, 307-326.
(19) McRee, D. E. In Practical Protein Crystallography; Academic Press: San
Diego, CA, 1993.
(20) Flack, H. D. Acta Crystallogr., Sect. A 1983, 39, 876.
JA0611137
9
7678 J. AM. CHEM. SOC. VOL. 128, NO. 23, 2006