Regioisomerically pure oxochlorins and methods of synthesis

Details Regioisomerically pure oxochlorins and methods of synthesis Regioisomerically pure oxochlorins and methods of synthesis

2001-12-07

2004-07-20

Raymond, Richard L. (Department: 1624)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

active

06765092

ABSTRACT:

FIELD OF THE INVENTION
The present invention concerns oxochlorin compounds, methods of making the same, and polymers, light harvesting arrays, and solar cells formed therefrom.
BACKGROUND OF THE INVENTION
The synthesis of light-harvesting rods can be achieved through use of porphyrinic building blocks. A major goal in the development of porphyrin or chlorin building blocks for application in light-harvesting systems is to fine-tune their photophysical and electrochemical properties. Tuning has been achieved with porphyrins by incorporating various substituents at the meso as well as &bgr;-positions, introduction of different core metals, etc. (Li, F. et al.,
J. Mater. Chem.
1997, 7, 1245-1262; Yang, S. I. et al.,
J. Porphyrins Phthalocyanines
1999, 3, 117-147; Yang, S. I. et al.,
J. Am. Chem. Soc.
1999, 121, 4008-4018). Chlorins have two considerable advantages for light-harvesting applications in comparison with porphyrins: (1) the extinction coefficient of the long-wavelength absorption band is greater than that of porphyrins (Chang, C. K. et al.,
Proc. Natl. Acad. Sci. USA,
1981, 78, 2652-2656; Stolzenberg, A. M. et al.,
J. Am. Chem. Soc.
1981, 103, 4763-4778), and (2) chlorins are linear oscillators whereas metalloporphyrins are planar oscillators. These differences make chlorins superior to porphyrins for use in photosynthetic systems. Chlorin building blocks are quite attractive for applications in light-harvesting systems. The important photochemical properties of chlorins have motivated the development of a number of new syntheses of these green pigments in the past few years (Taniguchi, M. et al.,
J. Org. Chem.
2001, 66, 7342-7354; Jacobi, P. A. et al.,
Org. Lett.
2001, 3, 831-834; Montforts, F.-P. et al.,
Angew. Chem. Int. Ed.
2000, 39, 599-601; Shea, K. M. et al.,
Tetrahedron.
2000, 56, 3139-3144; Burns, D. H. et al.,
Chem. Commun.
2000, 299-300; Strachan, J.-P. et al.,
J. Org. Chem.
2000, 65, 3160-3172; Balasubramanian, T. et al.,
J. Org. Chem.
2000, 65, 7919-7929; Krattinger, B. et al.,
J. Org. Chem.
1999, 1857-1867; Johnson, C. K. et al.,
Tetrahedron Lett.
1998, 39, 4619-4622; Mironov, A. F. et al.,
J. Chem. Soc. Perkin Trans.
1 1998, 3601-3608).
Chlorin dyads are of particular interest as benchmarks for assessing the extent of electronic communication and the rates and efficiency of energy transfer between chlorins. Nevertheless, relatively little attention had been paid to the synthesis and comparative studies of covalently linked chlorin dyads, because chlorins have limited stability and the synthesis of chlorin building blocks has been quite challenging. A number of chlorin dyads with various linkages and configurations have been prepared. These chlorin dyads are categorized in the following groups: (1) chlorins with electron acceptors for electron-transfer studies (Tkachenko, N. V. et al.,
J. Am. Chem. Soc.
1999, 121, 9378-9387; Malinen, P. K. et al.,
Liebigs Ann.
1997, 1801-1804; Abel, Y. et al.,
Tetrahedron Lett.
1997, 38, 1745-1748; Zheng, G. et al.,
Chem. Commun.
1999, 2469-2470; Lindsey, J. S. et al.,
J. Am. Chem. Soc.
1988, 110, 3610-3621), (2) chlorins possessing fused aromatic rings (Kozyrev, A. N. et al.,
Tetrahedron
2000, 56, 3353-3364; Silva, A. M. G. et al.,
Tetrahedron Lett.
2000, 41, 3065-3068; Johnson, C. K. et al.,
Tetrahedron Lett.
1998, 39, 4753-4756; Krattinger, B. et al.,
Chem. Commun.
1998, 757-756), (3) chlorin-porphyrin dyads for energy-transfer studies (Faustino, M. A. et al.,
Photochem. Photobiol.
2000, 72, 217-225; Zheng, G. et al.,
Tetrahedron Lett.
1997, 38, 2409-2412; Wasielewski, M. R. et al.,
Solar Energy Materials and Solar Cells
1995, 38, 127-134; Johnson, D. G. et al.,
J. Am. Chem. Soc.
1993, 115, 5692-5701; Zenkevich, E. I. et al.,
J. Luminescence
1997, 75, 229-244), (4) chlorins with accessory pigments (Kutzki, O. et al.,
Helv. Chim. Acta,
2000, 83, 2231-2245; Wedel, M. et al.,
J. Org. Chem.
2001, 1681-1687; Vicente, M. G. H. et al.,
Chem. Commun.
1998, 2355-2356), (5) chlorin-chlorin dimers (Arnold, D. P. et al.,
Tetrahedron
2001, 57, 1335-1345; Zheng, G. et al.,
J. Org. Chem.
2000, 65, 543-557; Osuka, A. et al.,
Heterocycles
1997, 44, 165-168; Jaquinod, L. et al.,
Angew. Chem. Int. Ed. Engl.
1996, 35, 1013-1016), (6) oxochlorin-containing dyads (Kessel, D. et al.,
Photochem. Photobiol.
1991, 53, 475-479; Osuka, A. et al.,
Bull. Chem. Soc. Jpn.
1995, 68, 262-276; Osuka, A. et al.,
J. Am. Chem. Soc.
1996, J18, 155-168).
The conversion of chlorins to oxochlorins has little effect on the spectral properties but renders the macrocycle more resistant to oxidation (Chang, C. K. et al.,
J. Am. Chem. Soc.
1986, 108, 1352-1354; Stolzenberg, A. M. et al.,
Inorg. Chem.
1986, 25, 983-991; Zaleski, J. M. et al.,
J. Phys. Chem.
1993, 97, 13206-13215; Osuka, A. et al.,
Bull. Chem. Soc. Jpn.
1993, 66, 3837-3839). The general approach for forming an oxochlorin employs treatment of a &bgr;-substituted porphyrin with a suitable oxidizing agent such as hydrogen peroxide followed by acid-catalyzed pinacol rearrangement of the resulting diol (Inhoffen, von H. et al.,
Liebigs Ann. Chem.
1969, 725, 167-176; Bonnet, R. et al.,
J. Chem. Soc. (C)
1969, 564-570; Chang, C. K.
Biochemistry
1980, 19, 1971-1976; Chang, C. K. et al.,
J. Org. Chem.
1986, 51, 2134-2137) or OsO
4
(Chang, C. K. et al.,
J. Org Chem.
1985, 50, 4989-4991; Chang, C. K. et al.,
Heterocyclic Chem.
1985, 22, 1739-1741; Chang, C. K. et al.,
J. Biol. Chem.
1986, 261, 8593-8596; Bruickner, C. et al.,
Tetrahedron Lett.
1995, 36, 3295-3298; Bruickner, C. et al.,
Tetrahedron Lett.
1995, 36, 9425-9428; Pandey, R. K. et al.,
J. Org. Chem.
1997, 62, 1463-1472). This procedure works well with those porphyrins that give rise to only one oxochlorin isomer. Although this method takes advantage of porphyrins as readily available starting materials, multiple oxochlorin isomers are obtained from porphyrins that possess any of the following structural features: (1) at least one of the four pyrrole rings bears substituents that are different from the others, in which case multiple products are formed due to the reaction of OSO
4
at different sites; (2) different substituents (e.g., methyl/ethyl) are present at the two &bgr;-positions of the pyrrole ring that is attacked by O
S
O
4
, in which case pinacol rearrangement gives multiple products; and (3) the presence of meso-substituents that cause the symmetry of the porphyrin to be less than four-fold, in which case pinacol rearrangement of the diol gives multiple products. Oxochlorins of the latter type have been incorporated in a few multi-pigment arrays for studies of energy and electron transfer (Osuka, A. et al.,
Bull. Chem. Soc. Jpn.
1995, 68, 262-276; Osuka, A. et al.,
J. Am. Chem. Soc.
1996, 118, 155-168).
SUMMARY OF THE INVENTION
A method of making an oxochlorin comprises the steps of oxidizing a chlorin to produce a mixture of hydroxychlorin and oxochlorin, and then oxidizing the hydroxychlorin in said mixture, preferably with DDQ, to produce a mixture consisting essentially of oxochlorin. The step of oxidizing a chlorin is carried out by exposing the chlorin to alumina, typically in the presence of an oxidizing agent such as air or alumina. The oxidizing steps may be carried out in an organic solvent such as toluene. The chlorin is preferably a C-methylated chlorin, and is preferably metalated.
Also disclosed herein are novel oxochlorin compounds, wherein the oxochlorin compounds are 5,15 trans-substituted or 10,20 trans-substituted with linking groups.
The foregoing and other objects and aspects of the present invention are explained in detail in the specification set forth below.


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