Citation: ZHONG Ai-Guo, HUANG Ling, LI Bai-Ling, JIANG Hua-Jiang, LIU Shu-Bin. Structure, Spectroscopy and Reactivity Properties of Helically Chiral Metal(II)-Bisdipyrrin Complexes[J]. Acta Physico-Chimica Sinica, ;2010, 26(10): 2763-2771. doi: 10.3866/PKU.WHXB20101005 shu

Structure, Spectroscopy and Reactivity Properties of Helically Chiral Metal(II)-Bisdipyrrin Complexes

1.
1. Department of Chemistry, Taizhou College, Linhai 317000, Zhejiang Province, P. R. China;
2. Research Computing Center,University of North Carolina, Chapel Hill, North Carolina 27599-3420, USA

Received Date: 10 June 2010
Available Online: 27 September 2010

The tetradentate coordination of bisdipyrrin ligands from cyclooctapyrroles with single and double metal cation metalations generates helical chirality and brings about recent research interests in supremolecular chemistry. In this study, eight divalent metal cations (M(II), M=Ca, Mg, Mn, Zn, Cu, Ni, Fe, Co) in the formation of the singly metalated complexes (1M) and binuclear metal complexes (2M) are systematically investigated to appreciate their structure, spectroscopy, and reactivity properties by using density functional theory (DFT), time-dependent DFT, and conceptual DFT approaches. Their bonding properties are analyzed by the natural bond orbital (NBO) analysis. The simulation results revealed that structure, spectroscopy, and reactivity features of the 1M and 2M complexes are markedly different from their precursor bisdipyrrin (1H) with a larger electrophilicity index, smaller chemical hardness, and distinctive dual descriptor. UV-Vis spectra show diminished peaks with red shifts due to metalation.A few linear structure-reactivity relationships stemmed from these structure and reactivity properties have been obtained with the correlation coefficient (R²) between 0.858 and 0.986. The results can provide in-depth insights for these complexes from structure and reactivity viewpoints.
- Electronic spectrum,
- Bisdipyrrin,
- Metalloporphyrin,
- Helix molecular,
- Density functional theory
1. [1]
  
  1. (a) Gust, D.; Moore, T. A.; Moore, A. L. Acc. Chem. Res., 2001, 34: 40 (b) Bart, M. N.; Suijkerbuijk, R. K. Angew. Chem. Int. Edit., 2008, 47: 7396 (c) Collman, J. P.; Fu, L. Acc. Chem. Res., 1999, 32: 455
2. [2]
  2. (a) Meunier, B. Chem. Rev., 1992, 92: 1411 (b) Gust, D.; Moore, T. A.; Moore; A. L. Pure Appl. Chem., 1998, 70: 2189
3. [3]
  3. (a) Sharman, W. M.; Van Lier, J. E. Drug Discovery Today, 1999, 4: 507 (b) Refael, M.; Hana, W.; Youngjae, Y. J. Phys. Chem. B, 2008, 112: 3268
4. [4]
  4. (a) Haridas, V.; Harinder, S.; Yogesh, K.; Kashmiri, L. J. Chem. Sci., 2007, 119: 219 (b) Pushpan, S. K.; Venkatraman, S.; Anand, V. G.; Sankar, J.; Rath, H.; Chandrasheka, T. K. Proc. Indian Acad. Sci. (Chem. Sci.), 2002, 114: 311
5. [5]
  5. Dollphin, D. The porphyrins. NewYork: Academic Press, 1978: 240
6. [6]
  6. Sessler, J. L.; Weghorn, S. J. Expanded, contracted and isomeric porphyrins. Oxford: Elsevier, 1997: 520
7. [7]
  7. (a) Buchecker, C. O.; Sauvage, J. P. Angew. Chem. Int. Edit., 1989, 28: 189 (b) Buchecker, C. O.; Guilhemj, P. C.; Sauvage, J. P. Angew. Chem. Int. Edit., 1990, 29: 1154 (c) Buchecker, C. O.; Nierengarten, J. F.; Sauvage, J. P.; Armaroli, N.; Balzani, V.; Cola, L. D. J. Am. Chem. Soc., 1993, 115: 11237
8. [8]
  8. Vogel, E.; Bröring, M.; Fink, J.; Rosen, D.; Schmickler, H.; Lex, J.; Chan, K.; Wu, Y. D.; Plattner, D. A.; Nendel, M.; Houk, K. N. Angew. Chem. Int. Edit., 1995, 34: 2511
9. [9]
  9. Werner, A.; Michels, M.; Zander, L.; Lex, J.; Vogel, E. Angew. Chem. Int. Edit., 1999, 38: 3650
10. [10]
  10. Setsune, J.; Tsukajima, A.; Okazaki, N.; Lintuluoto, J. M.; Lintuluoto, M. Angew. Chem. Int. Edit., 2009, 48: 771
11. [11]
  11. (a) Lexander, G.; Vogel, E.; Jonathan, L. Chemical Physics, 2002, 282: 37 (b) Punnagai, M.; Hari, S. J. Mol. Struct.-Theochem, 2004, 684: 21 (c) Katsunori, N.; Kei, K.; Atsuhiro, O. J. Inorg. Biochem., 2008, 102: 466 (d) Deng, W. Y.; Qiu, W. Y. J. Mol. Struct., 2008, 875: 515
12. [12]
  12. Amanda, J. M.;William, D. K.; Hiroshi, F.; David, P. G. J. Am. Chem. Soc., 2009, 131: 8040
13. [13]
  13. John, M.; Martin, J.; Stillman, N. K. Coord. Chem. Rev, 2007, 251: 429
14. [14]
  14. (a) Parr, R. G.; Yang,W. T. Density functional theory of atoms and molecules. NewYork: Oxford University Press, 1989 (b) Geerlings, P.; De Proft, F.; Langenaeker, W. Chem. Rev., 2003, 103: 1793 (c) Chermette, H. J. Comput. Chem., 1999, 20: 129
15. [15]
  15. (a) Rong, C. Y.; Lian, S. X.; Yin, D. L.; Zhong, A. G.; Zhang, R. Q.; Liu, S. B. Chem. Phys. Lett., 2007, 434: 149 (b) Xia, Y.; Yin, D. L.; Rong, C. Y.; Xu, Q.; Yin, D. H.; Liu, S. B. J. Phys. Chem. A, 2008, 112: 9970
16. [16]
  16. (a) Parr, R. G.; Szentpaly, L. V.; Liu, S. B. J. Am. Chem. Soc., 1999, 105: 1922 (b) Liu, S. B.; Parr, R. G. J. Chem. Phys., 1997, 106: 5578
17. [17]
  17. Mulliken, R. S. J. Chem. Phys., 1934, 2: 782
18. [18]
  18. Pearson, R. G. J. Am. Chem. Soc., 1963, 85: 3533
19. [19]
  19. Liu, S. B.; vind, N. J. Phys. Chem. A, 2008, 112: 6690
20. [20]
  20. Liu, S. B. Electrophilicity//Chattaraj, P. K. Chemical reactivity theory: a density functional theory view. London: Taylor& Francis Group, 2009
21. [21]
  21. Zhang, J.; Hu, S. Q.; Wang, Y.; Guo, W. Y.; Liu, J. X.; You, L. Acta Chimica Sinica, 2008, 66: 2469 [张军,胡松青,王勇, 郭文跃,刘金祥, 尤龙.化学学报, 2008, 66: 2469]
22. [22]
  22. Liu, S. B. Acta Phys. -Chim. Sin., 2009, 25: 590 [刘述斌.物理化学学报, 2009, 25: 590]
23. [23]
  23. Frisch, M. J.; Trucks, G. W.; Schlegel. H. B.; et al. Gaussian 03 Revision D.02. Pittsburgh, PA: Gaussian Inc., 2003
24. [24]
  24. Huang, Y.; Zhong, A. G.; Rong, C. Y.; Xiao, X. M.; Liu, S. B. J. Phys. Chem. A, 2008, 112: 305
25. [25]
  25. Zhong, A. G.; Wu, J. Y.; Yan, H.; Jin, Y. X.; Dai, G. L.; Jiang, H. J.; Pan, F. Y.; Liu, S. B. Acta Phys. -Chim. Sin., 2009, 24: 1367 [钟爱国,吴俊勇, 闫华, 金燕仙,戴国梁,蒋华江, 潘富友,刘述斌. 物理化学学报, 2009, 24: 1367]
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