Cross-conjugated bis(porphryin)s: Synthesis, electrochemical behavior, mixed valency, and biradical dication formation

Journal of Organic Chemistry

Volumn 64, Issue 25, 1999, Pages 9124-9136

  Shultz, David A ^a   Lee, Hyoyoung ^a,b   Kumar, R Krishna ^a   Gwaltney, Kevin P ^a  

^a NORTH CAROLINA STATE UNIVERSITY   (United States)

^b Pohang University of Science and Technology (POSTECH)   (South Korea)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE DERIVATIVE; PORPHYRIN DERIVATIVE; ZINC DERIVATIVE;

ARTICLE; CHEMICAL BOND; CHEMICAL INTERACTION; CHEMICAL REACTION; CHEMICAL STRUCTURE; ELECTROCHEMISTRY; OXIDATION REDUCTION REACTION; SPECTRAL SENSITIVITY; SYNTHESIS;

EID: 0032761409     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo991046h     Document Type: Article

References (129)

1. Iwamura, H. Adv. Phys. Org. Chem. 1990, 26, 179.
2. Koga, N.; Iwamura, H. Nihon Kagaku Kaishi 1989, 1456.
3. Kamachi, M. Nihon Butsuri Gakkaishi 1987, 42, 351.
4. Kitano, M.; Koga, N.; Iwamura, H. J. Chem. Soc., Chem. Commun. 1994, 447.
5. Miller, J. S.; Calabrese, J. C.; McLean, R. S.; Epstein, A. J. Adv. Mater. 1992, 4, 498.
6. Böhm, A.; Vazquez, C.; McLean, R.; Calabrese, J.; Kalm, S.; Manson, J.; Epstein, A.; Miller, J. Inorg. Chem. 1996, 35, 3083.
7. Brandon, E. J.; Kollmar, C.; Miller, J. S. J. Am. Chem. Soc. 1998, 120, 1822.
8. Brandon, E. J.; Arif, A. M.; Burkhart, B. M.; Miller, J. S. Inorg. Chem. 1998, 37, 2792.
9. Brinckerhoff, W. B.; Morin, B. G.; Brandon, E. J.; Miller, J. S.; Epstein, A. J. J. Appl. Phys. 1996, 83, 6974.
10. Buschmann, W.; Vazquez, C.; Ward, M.; Jones, N.; Miller, J. Chem. Commun. 1997, 409.
11. Girtu, N. A.; Wynn, C. M.; Sugiura, K.-I.; Miller, J. S.; Epstein, A. J. Synth. Met. 1997, 85, 1703.
12. Epstein, A. J.; Miller, J. S. Synth. Met. 1996, 80, 231.
13. Molecular Magnetism: From Molecular Assemblies to the Devices; Coronado, E.; Delhaes, P., Gatteschi, D., Miller, J. S., Eds.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1996; Vol. 321.
14. Yates, M. L.; Arif, A. M.; Manson, J. L.; Kalm, B. A.; Burkhart, B. M.; Miller, J. S. Inorg. Chem. 1998, 37, 840.
15. Wynn, C. M.; Girtu, M. A.; Brinckerhoff, W. B.; Sugiura, K.-I.; Miller, J. S.; Epstein, A. J. Chem. Mater. 1997, 9, 2156.
16. Miller, J. S.; Vazquez, C.; Epstein, A. J. J. Mater. Chem. 1995, 5, 707.
17. Miller, J. S.; Epstein, A. J. Angew. Chem., Int. Ed. Engl. 1994, 33, 385.
18. Shultz, D. A.; Lee, H.; Gwaltney, K. P.; Sandberg, K. A. Mol. Cryst. Liq. Cryst. 1999, 334, 459.
19. Shultz, D. A.; Lee, H.; Gwaltney, K. P. J. Org. Chem. 1998, 63, 7584.
20. Shultz, D. A.; Gwaltney, K. P.; Lee, H. J. Org. Chem. 1998, 63, 4034.
21. Lindsey, J. S.; Prathapan, S.; Johnson, T. E.; Wagner, R. W. Tetrahedron 1994, 50, 8941.
22. Sasaki, S.; Iyoda, M. Chem. Lett. 1995, 11, 1011.
23. Shultz, D. A.; Gwaltney, K. P.; Lee, H. J. Org. Chem. 1998, 63, 769.
24. Yang, S. I.; Lammi, R. K.; Seth, J.; Riggs, J. A.; Arai, T.; Kim, D.; Bocian, D. F.; Holten, D.; Lindsey, J. S. J. Phys. Chem. B 1998, 702, 9426.
25. Ishiyama, T.; Murata, M.; Miyaura, N. J. Org. Chem. 1995, 60, 7508.
26. Kohn, M.; Löff, G. Monatsh. Chem. 1924, 45, 589.
27. Ishida, T.; Iwamura, H. J. Am. Chem. Soc. 1991, 113, 4238.
28. See the Supporting Information for spectroscopic and crystallographic data.
29. Shultz, D. A.; Sandberg, K. A. J. Phys. Org. Chem. 1999, 12, 10.
30. Scheidt, W. R.; Lee, Y. J. In Structure and Bonding, Vol. 64; Buchler, J. W., Ed.; Springer-Verlag: Berlin, 1987; pp 1-70.
31. Fajer, J.; Borg, D. C.; Forman, A.; Dolphin, D.; Felton, R. H. J. Am. Chem. Soc. 1970, 92, 3451.
32. Atamian, M.; Wagner, R. W.; Lindsey, J. L.; Bocian, D. F. Inorg. Chem. 1988, 27, 1510.
33. Prendergast, K.; Spiro, T. G. J. Phys. Chem. 1991, 95, 9728.
34. Skillman, A. G.; Collins, J. R.; Loew, G. H. J. Am. Chem. Soc. 1992, 114, 9538.
35. Song, H.; Reed, C. A.; Scheidt, W. R. J. Am. Chem. Soc. 1989, 111, 6865.
36. Erler, B. S.; Scholz, W. F.; Lee, Y. L.; Scheidt, W. R.; Reed, C. A. J. Am. Chem. Soc. 1987, 109, 2644.
37. Fujii, H. Inorg. Chem. 1993, 32, 875.
38. Fujii, H. J. Am. Chem. Soc. 1993, 115, 4641.
39. (a) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999.
40. (b) West, A. P., Jr.; Silverman, S. K.; Dougherty, D. A. J. Am. Chem. Soc. 1996, 118, 1452.
41. (c) Borden, W. T.; Davidson, E. R. Acc. Chem. Res. 1996, 29, 67.
42. (d) Li, S.; Ma, J.; Jiang, Y. J. Phys. Chem. 1996, 100, 4775.
43. (e) Rajca, A. Chem. Rev. 1994, 94, 871.
44. (f) Ichimura, A.; Koga, N.; Iwamura, H. J. Phys. Org. Chem. 1994, 7, 207.
45. (g) Borden, W. T.; Iwamura, H.; Berson, J. A. Acc. Chem. Res. 1994, 24, 109.
46. (h) Iwamura, H. Pure Appl. Chem. 1993, 65, 57.
47. (i) Iwamura, H.; Koga, N. Acc. Chem. Res. 1993, 26, 346.
48. (j) Dougherty, D. A.; Jacobs, S. J.; Silverman, S. K.; Murray, M.; Shultz, D. A.; West, A. P., Jr.; Clites, J. A. Mol. Cryst. Liq. Cryst. 1993, 232, 289.
49. (k) Jacobs, S. J.; Shultz, D. A.; Jain, R.; Novak, J.; Dougherty, D. A. J. Am. Chem. Soc. 1993, 115, 1744.
50. (l) Dougherty, D. A. Acc. Chem. Res. 1991, 24, 88.
51. (m) Iwamura, H. Adv. Phys. Org. Chem. 1990, 26, 179.
52. (n) Kinetics and Spectroscopy of Carbenes and Biradicals; Platz, M. S., Ed.; Plenum Press: 1990.
53. (o) Iwamura, H. Pure Appl. Chem. 1987, 59, 1595.
54. (p) Goldberg, A. H.; Dougherty, D. A. J. Am. Chem. Soc. 1983, 105, 284.
55. (q) Berson, J. A. Diradicals; Wiley: New York, 1982.
56. (r) Borden, W. T.; Davidson, E. R. Acc. Chem. Res. 1981, 14, 69.
57. (s) Borden, W. T.; Davidson, E. R. J. Am. Chem. Soc. 1977, 99, 4587.
58. Borden, W. T.; Davidson, E. R. J. Am. Chem. Soc. 1977, 99, 4587.
59. Kollmar, H.; Staemmler, V. Theor. Chim. Acta (Berlin) 1978, 48, 223.
60. Karafiloglou, P. J. Chem. Phys. 1985, 82, 3728.
61. LeCours, S. M.; DiMagno, S. G.; Therien, M. J. J. Am. Chem. Soc. 1996, 118, 11854.
62. Computational results corroborate our hypothesis: Shultz, D. A.; Sandberg, K. A.; Dilday, J. S. J. Phys. Chem., to be submitted.
63. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
64. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
65. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
66. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
67. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
68. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
69. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
70. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
71. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
72. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
73. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
74. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
75. For papers discussing the effects of torsion on exchange coupling, see: (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847. (c) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273. (d) Okada, K.; Matsumoto, K.; Oda, M.; Murai, H.; Akiyama, K.; Ikegami, Y. Tetrahedron Lett. 1995, 36, 6693. (e) Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974. (f) Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347. (g) Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047. (h) Barone, V.; Bencini, A.; di Matteo, A. J. Am. Chem. Soc. 1997, 119, 10831. (i) Nakazono, S.; Karasawa, S.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1998, 37, 1550. (j) Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386. (k) Shultz, D. A. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999. (l) Ab initio calculations explain antiferromagnetic coupling in m-phenylene-linked structures; see: Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727. (m) For several beautiful examples of conformational J modulation in metal complexes exchange coupled through organic ligands, see: McCleverty, J. A.; Ward, M. D. Acc. Chem. Res. 1998, 31, 842.
76. Sessler reported a gable bis(porphyrin) in which the porphyrin rings were twisted 55° relative to the m-phenylene coupler: Sessler, J. L.; Johnson, M. R.; Creager, S. E.; Fettinger, J. C.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 9310.
77. Zhou, Q.; Swager, T. M. J. Org. Chem. 1995, 60, 7096.
78. Robin, M. B.; Day, P. Adv. Inorg. Radiochem. 1967, 10, 247.
79. Bonvoisin, J.; Launay, J. P.; Rovira, C.; Veciana, J. Angew. Chem., Int. Ed. Engl. 1994, 33, 2106.
80. Bonvoisin, J.; Launay, J. P.; Vanderauweraer, M.; DeSchryver, F. C. J. Phys. Chem. 1994, 98, 5052.
81. Bonvoisin, J.; Launay, J. P.; Verbouwe, W.; Vanderauweraer, M.; DeSchryver, F. C. J. Phys. Chem. 1996, 100, 17079.
82. Coronado, E.; Galan-Mascaros, J. R.; Gimenez-Saiz, C.; Gomez-Garcia, C. J.; Triki, S. J. Am. Chem. Soc. 1998, 120, 4671.
83. Domingo, V. M.; Castaner, J. J. Chem. Soc., Chem. Commun. 1995, 895.
84. Domingo, V. M.; Castañer, J.; Riera, J.; Brillas, E.; Molins, E.; Martinez, B.; Knight, B. Chem. Mater. 1997, 9, 1620.
85. Karafiloglou, P.; Launay, J. P. J. Phys. Chem. A 1998, 102, 8004.
86. Le Mest, Y.; L'Her, M.; Hendricks, N. H.; Kim, K.; Collman, J. P. Inorg. Chem. 1992, 31, 835.
87. Rajca, S.; Rajca, A. J. Am. Chem. Soc. 1995, 117, 9172.
88. Sedó, J.; Ruiz, D.; VidalGancedo, J.; Rovira, C. J.; Bonvoisin, J.; Launay, J. P.; Veciana, J. Adv. Mater. 1996, 8, 748.
89. Sedó, J.; Ruiz, D.; VidalGancedo, J.; Rovira, C. J.; Bonvoisin, J.; Launay, J. P.; Veciana, J. Mol. Cryst. Liq. Cryst. 1997, A306, 125.
90. Sedó, J.; Ruiz, D.; VidalGancedo, J.; Rovira, C. J.; Bonvoisin, J.; Launay, J. P.; Veciana, J. Synth. Met. 1997, 85, 1651.
91. Utamapanya, S.; Rajca, A. J. Am. Chem. Soc. 1991, 113, 9242.
92. Sutton, J. E.; Taube, H. Inorg. Chem. 1981, 20, 3125.
93. Ferrere, S.; Elliot, C. M. Inorg. Chem. 1995, 34, 5818 and references therein.
94. An alternative possibility would be charge-spin separation (for examples of charge-spin separation, see: Niemz, A.; Rotello, V. M. J. Am. Chem. Soc. 1997, 119, 6833. Wudl, F. J. Am. Chem. Soc. 1981, 703, 7064). In this case, charge density would increase in the coupler, but spin density would not increase in the coupler. Thus, electron- poor couplers might more strongly couple radical cations. Either way, substituent effects could modulate exchange coupling.
95. An alternative possibility would be charge-spin separation (for examples of charge-spin separation, see: Niemz, A.; Rotello, V. M. J. Am. Chem. Soc. 1997, 119, 6833. Wudl, F. J. Am. Chem. Soc. 1981, 703, 7064). In this case, charge density would increase in the coupler, but spin density would not increase in the coupler. Thus, electron-poor couplers might more strongly couple radical cations. Either way, substituent effects could modulate exchange coupling.
96. Tabushi, I.; Sasaki, T. Tetrahedron Lett. 1982, 23, 1913.
97. .+ is greater.
98. Ward, M. D. Chem. Soc. Rev. 1995, 121.
99. Davis, W. B.; Svec, W. A.; Ratner, M. A.; Wasielewski, M. R. Nature 1998, 396, 60.
100. The Porphyrins; Dolphin, D., Ed.; Academic Press: New York, 1978; Vols. 1-7.
101. Brancato-Buentello, K. E.; Kang, S.-J.; Scheidt, W. R. J. Am. Chem. Soc. 1997, 119, 2839.
102. 1/2/RT)}.
103. Hush, N. S. Prog. Inorg. Chem. 1967, 8, 301.
104. Haberkorn, R.; Michelbeyerle, M. E.; Marcus, R. A. Proc. Natl. Acad. Sci. U.S.A. 1979, 76, 4185.
105. Binstead, R. A.; Hush, N. S. J. Phys. Chem. 1993, 97, 13172.
106. Breton, J.; Nabedryk, E.; Parson, W. W. Biochemistry 1992, 31, 7503.
107. Gasyna, Z.; Schatz, P. N. J. Phys. Chem. 1996, 100, 1445.
108. Lendzian, F.; Huber, M.; Isaacson, R. A.; Endeward, B.; Plato, M.; Bonigk, B.; Mobius, K.; Lubitz, W.; Feher, G. Biochim. Biophys. Acta 1993, 1183, 139.
109. Osuka, A.; Maruyama, K. Chem. Lett. 1987, 825.
110. Reimers, J. R.; Hush, N. S. Inorg. Chim. Acta 1994, 226, 33.
111. Reimers, J. R.; Hush, N. S. Chem. Phys. 1995, 197, 323.
112. Reimers, J. R.; Hutter, M. C.; Hush, N. S. Photosynth. Res. 1998, 55, 163.
113. Scheidt, W. R.; Cheng, B. S.; Haller, K. J.; Mislankar, A.; Rae, A. D.; Reddy, K. V.; Song, H. S.; Orosz, R. D.; Reed, C. A.; Cukiernik, F.; Marchon, J. C. J. Am. Chem. Soc. 1993, 115, 1181.
114. Stocker, J. W.; Hug, S.; Boxer, S. G. Biochim. Biophys. Acta 1993, 1144, 325.
115. Wynne, K.; Haran, G.; Reid, G. D.; Moser, C. C.; Dutton, P. L.; Hochstrasser, R. M. J. Phys. Chem. 1996, 100, 5140.
116. 1u-like. However, this should alter neither the fact that the two unpaired electrons are delocalized in porphyrin planes that are ca. 5 Å apart, nor the validity of the D-value estimate.
117. Keana, J. F.; Dinerstein, R. J. J. Am. Chem. Soc. 1971, 93, 2808.
118. Weissman, S. I.; Kothe, G. J. Am. Chem. Soc. 1975, 97, 2537.
119. An alteration of Keana's relationship (ref 86) is necessary for accurate estimation of interelectronic separation in dinitroxide biradicals. Gleason, W. B.; Barnett, R. E. J. Am. Chem. Soc. 1976, 98, 2701. Perhaps in the present cases, neither relationship accurately correlates r and |D/hc|.
120. Berson, J. A. Diradicals; Wiley: New York, 1982.
121. Kahn, O. Molecular Magnetism; VCH: New York, 1993.
122. Rajca, A. Chem. Rev. 1994, 94, 871.
123. Mitsumori, T.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1995, 117, 2467.
124. Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Phys. Chem. 1993, 97, 13267.
125. Akita, T.; Mazaki, Y.; Kobayashi, D.; Koga, N.; Iwamura, H. J. Org. Chem. 1995, 60, 2092.
126. Yoshioka, N.; Lahti, P. M.; Kaneko, T.; Kuzumaki, Y.; Tsuchida, E.; Nishide, H. J. Org. Chem. 1994, 59, 4272.
127. Carilla, J.; Juliá, L.; Riera, J.; Brillas, E.; Garrido, J. A.; Labarta, A.; Alcalá, R. J. Am. Chem. Soc. 1991, 113, 8281.
128. Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273.
129. Shultz, D. A.; Farmer, G. T. J. Org. Chem. 1998, 63, 6254.