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The porphyrin handbook - Kadish K.M.

Kadish K.M. The porphyrin handbook - Academic press, 2000. - 368 p.
Download (direct link): kadishsmishgulilard2000.djvu
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cofacial orientation.239 The structure is confirmed in the solid state by
X-ray analyses and in solution by the EPR analyses of Cu(II) ion. In the
solid state, the pair of stacked porphyrin subunits adopts a shared
relationship, with the Cu atoms being offset by about 3.05 A and the Cu-
Cu separation of 4.76 A. In addition to conventional n-n stacking between
the porphyrin nuclei, the assembly is stabilized via [N + -H- O] and
[C-H- O] hydrogen bonding between the dibenzylammonium centers attached
to the porphyrin hub, and the oxygen atoms of polyether binders. The
distance between the Cu(II) centers in the dynamic equilibrium state is
evaluated to be 5.1 A from the EPR spectra, which represents an upper
limit for the complex's Cu-Cu distance.
All examples shown here demonstrate that self-assembling procedures
provide unique and promising methods for construction of highly ordered,
but very complex, multiporphyrin systems which are difficult to prepare
by conventional covalent syntheses. It should be noted that properly
designed self-assembling systems execute difficult processes such as
tetra- or more molecular assembling process which appear to be extremely
unfavorable due to their large entropic disadvantage. The energy to
ensure the necessary stability of the assembly must be supplied from the
enthalpy gain during the assembling processes. Since the proper balance
between the entropy and enthalpy changes in the assembling processes can
be regulated by selecting the number and types of interactions between
the components, it is important to develop systematic methodology for
manipulation of various kinds of noncovalent interactions found in both
chemistry and biochemistry. Another interesting and important problem to
resolve is the effect of
noncovalent bonds on the efficiencies of the energy or electron-transfer
processes occurring in the multiporphyrin assemblies. There is not
sufficient information on how much contribution of "through-bond"
transfer is expected for noncovalent interactions and whether the
characteristics of the transfer processes depend on the type of
interaction. From these viewpoints it is clear there are still a large
number of possibilities remaining that should be attempted in the field
of self-assembling multiporphyrin chemistry.

REFERENCES
1. Morgan, B.; Dolphin, D. Synthesis and Structure of Biomimetic
Porphyrins', Morgan, B.; Dolphin, D" Eds.; Springer-Verlag: Berlin, 1987;
Vol. 64, p. 115.
2. Sessler, J. L.; Wang, B.; Springs, S. L.; Brown, . T.
Comprehensive Supramolecular Chemistry, Y. Marakami, Ed, Oxford, 1996;
Vol. 4, p. 311.
3. Hayashi, .; Ogoshi, H. Chem. Soc. Rev. 1997, 26, 355.
4. Wasielewski, M. R. Chem. Rev. 1992, 92, 435.
5. Kurreck, H.; Huber, M. Angew. Chem. Int. Ed. Engl. 1995, 34, 849.
6. Ogoshi, H.; Mizutani, T. Acc. Chem. Res. 1998, 31, 81.
7. Lautsch, W.; Pasedag, R.; Sommer, I.; Julius, H. J.; Boederfeld, E.
Chimica (Switz) 1959, 13, 129.
8. Lautsch, W.; Wiemer, B.; Zschenderlein, P.; Kraege, H. J.; Bandel,
W.; Gunther, D.; Schultz, G.; Gnichtel, H. KolioidZ. 1958, 161, 36.
9. Hayashi, .; Takimura, .; Ogoshi, H. J. Am. Chem. Soc. 1995, 117,
11606.
10. Suzuki, A.; Okuda, K.; Kawagoe, K.; Toi, H.; Aoyama, Y.; Ogoshi, H.
Chem. Lett. 1985, 1169.
11. Hamachi, I.; Tajiri, Y.; Shinkai, S. J. Am. Chem. Soc. 1994, 116,
7437.
12. Hamachi, I.; Tajiri, Y.; Nagase, .; Shinkai, S. Eur. J. Chem.
1997, 3. 1025.
13. Murakami, H,; Nagasaki, .; Hamachi, 1.; Shinkai, S. Tetrahedron
Lett. 1993, 34, 6273.
14. Hayashi, .; Miyahara, .; Koide, N.; Kato, Y.; Masuda, H.; Ogoshi,
H. J. Am. Chem. Soc. 1997. 119, 7281.
46 / Porphyrins and Metalloporphyrins as Receptor Models
337
15. Setsune. J.: Hashimolo. M; Shio/awa, K.: Hayakawa, J.; Ochi. .;
Masuda. R. Tetrahedron 1998, 54, 1407.
16. Ogoshi, H.: Hma. .; Kato. V.; Mizutani. .; Kuroda. V. Supramol.
Client. 1995, 6. 115.
17. Mi/ulani. .: Ema. .; Tomita, .; Kuroda. Y.; Ogoshi. H. ./. Chem.
Soc., Chem. Commun. 1993, 520.
18. Mizulani. Hma. .; Iomita. .; Kuroda, Y.; Ogoshi. H. ./. Am Chem.
Soc. !994. /16. 4240.
10. Milbradt, R.; Weiss. J. Temihedron Lett. 1995. 36. 2999.
20. Mi/.uuini. .: I.; Yoshida. .; Kuroda, Y.; Ogoshi, H fnorg.
Chem. 1993, 32, 2072.
21. Mi/.utam. .; Hma, .; Yoshida, .; Rcnnc, .; Ogoshi, H, Inorg.
Chem. 1994. 33, 3558.
22. Mi/ulani, .; Kurahashi. .: Murakami. .: Matsumi, N.; Ogoshi. H.
J. Am. Chem. Soc. 1997, 119, 8991.
23. Havashi. .; Asai. .: Hoka/ono. H.; Ogoshi, H. J. Am. Chem. Soc.
1993. 115, 12210.
24. Kuroda. Y.: Kawashima. A.; Havashi. Y.: Ogoshi, H. ./. Am. Chem.
Soc. 1997, 119, 4929.
25. Havashi, .; Asai, .; Borgmeier, .; Hokazono. H.; Ogoshi. H.
Chem. Eitr. J 1998, 4. 1266.
26. Kuroda, Y.; Kawashima. A.; Urai. .; Ogoshi, H. Tetrahedron Lett.
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