Nonplanar, noninnocent, and chiral: A strongly saddled metallocorrole

Inorganic Chemistry

Volumn 49, Issue 17, 2010, Pages 7608-7610

  Alemayehu, Abraham B ^a   Hansen, Lars Kristian ^a   Ghosh, Abhik ^a  

^a UNIVERSITY OF TROMSØ   (Norway)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 77956195361     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic1008736     Document Type: Article

References (31)

1. Alemayehu, A. B., Gonzalez, E., Hansen, L.-K., and Ghosh, A. Inorg. Chem. 2009, 48, 7794-7799
2. Paolesse, R., Nardis, S., Sagone, F, and Khoury, R. G. J. Org. Chem. 2001, 66, 550-556
3. Palmer, J. H., Day, M. W., Wilson, A. D., Henling, L. M., Gross, Z., and Gray, H. B. J. Am. Chem. Soc. 2008, 130, 7786-7787
4. Palmer, J. H., Mahammed, A., Lancaster, K. M., Gross, Z., and Gray, H. B. Inorg. Chem. 2009, 48, 9308-9315
5. Ligand noninnocence is ubiquitous for metallocorroles. For key studies, see: Cai, S., Walker, F. A., and Licoccia, S. Inorg. Chem. 2000, 39, 3466-3478
6. Ghosh, A., Wondimagegn, T., and Parusel, A. B. J. J. Am. Chem. Soc. 2000, 122, 5100-5104
7. Steene, E., Wondimagegn, T., and Ghosh, A. J. Phys. Chem. B 2001, 105, 11406-11413
8. Addition/correction: J. Phys. Chem. B 2002, 106, 5312.
9. Zakharieva, O., Schünemann, V., Gerdan, M., Licoccia, S., Cai, S., Walker, F. A., and Trautwein, A. X. J. Am. Chem. Soc. 2002, 124, 6636-6648
10. Steene, E., Dey, A., and Ghosh, A. J. Am. Chem. Soc. 2003, 125, 16300-16309
11. Walker, F. A., Licoccia, S., and Paolesse, R. J. Inorg. Biochem. 2006, 100, 810-837
12. Roos, B. O., Veryazov, V., Conradie, J., Taylor, P. R., and Ghosh, A. J. Phys. Chem. 2008, 112, 14099-14102
13. For other examples of copper corrole X-ray structures, see: Brückner, C., Brinas, R. P., and Bauer, J. A. K. Inorg. Chem. 2003, 42, 4495-4497
14. Luobeznova, I., Simkhovich, L., Goldberg, I., and Gross, Z. Eur. J. Inorg. Chem. 2004, 1724-1732
15. Bröring, M., Bregier, F., Tejero, E. C., Hell, C., Hell, C., and Holthausen, M. C. Angew. Chem., Int. Ed. 2007, 46, 445-448
16. For key references to β-octabromo- meso -tetraarylporphyrin derivatives, see: Renner, M. W., Barkigia, K. M., Zhang, Y., Medforth, C. J., Smith, K. M., and Fajer, J. J. Am. Chem. Soc. 1994, 116, 8582-8592
17. Ghosh, A., Halvorsen, I., Nilsen, H. J., Steene, E., Wondimagegn, T., Lie, R., van Caemelbecke, E., Guo, N., Ou, Z. P., and Kadish, K. M. J. Phys. Chem. B 2001, 105, 8120-8124
18. Henling, L. M., Schaefer, W. P., Hodge, J. A., Hughes, M. E., Gray, H. B., Lyons, J. E., and Ellis, P. E. Acta Crystallogr., Sect. E 1993, 49, 1743-1747
19. Shao, J. L., Steene, E., Hoffman, B. M., and Ghosh, A. Eur. J. Inorg. Chem. 2005, 1609-1615
20. III center and a corrole radical: Nardis, S., Paolesse, R., Licoccia, S., Fronczek, F. R., Vicente, M. G. H., Shokhireva, T. K., Cai, S., and Walker, F. A. Inorg. Chem. 2005, 44, 7030-7046
21. For key electronic absorption spectroscopic and spectroelectrochemical studies of copper corroles, see: Wasbotten, I. H., Wondimagegn, T., and Ghosh, A. J. Am. Chem. Soc. 2002, 124, 8104-8116
22. Ou, Z., Shao, J., Zhao, H., Ohkubo, K., Wasbotten, I. H., Fukuzumi, S., Ghosh, A., and Kadish, K. M. J. Porphyrins Phthalocyanines 2004, 8, 1236-1247
23. Thomas, K. E., Wasbotten, I. H., and Ghosh, A. Inorg. Chem. 2008, 47, 10469-10478
24. Although nonplanar porphyrins generally exhibit red-shifted optical spectra, the exact origin of the red shifts is a remarkably subtle issue. DiMagno and co-workers have shown that the ruffling distortion per se does not lead to red-shifted spectra. Yet, calculations on the actual skeletons of nonplanar porphyrins do show red-shifted spectra. The solution to this conundrum appears to be that distortions along higher-frequency modes (i.e., various kinked dihedrals), as distinct from ruffling per se, lead to the observed red shifts: Wertsching, A. K., Koch, A. S., and DiMagno, S. G. J. Am. Chem. Soc. 2001, 123, 3932-3939
25. Parusel, A. B. J., Wondimagegn, T., and Ghosh, A. J. Am. Chem. Soc. 2000, 122, 6371-6374
26. Haddad, R. E., Gazeau, S., Pécaut, J., Marchon, J.-C., Medforth, C. J., and Shelnutt, J. A. J. Am. Chem. Soc. 2003, 125, 1253-1268
27. Wasbotten, I. H., Conradie, J., and Ghosh, A. J. Phys. Chem. B 2003, 107, 3613-3623
28. We have commented elsewhere (8) on the fact that meso -aryl substituents exert far more dramatic effects on the Soret maxima of copper corroles than they do for other metals. This study provides a plausible qualitative explanation of this phenomenon. Copper corroles, because of their potentially strongly saddled geometries, sustain much stronger orbital overlaps between the corrole core and meso -aryl groups than do other metallocorroles.
29. 1/2red = 0.05 V.
30. The OLYP exchange-correlation functional is based on the OPTX exchange functional (Handy, N. C. and Cohen, A. J. Mol. Phys. 2001, 99, 403-412) and the LYP correlation functional (Lee, C., Yang, W., and Parr, R. G. Phys. Rev. 1988, B37, 785-789).
31. The calculations were carried out with the ADF program system with methods described in: Velde, G. T., Bickelhaupt, F. M., Baerends, E. J., Guerra, C. F., Van Gisbergen, S. J. A., Snijders, J. G., and Ziegler, T. J. Comput. Chem. 2001, 22, 931-967