Acta Phys. -Chim. Sin. ›› 2010, Vol. 26 ›› Issue (10): 2763-2771.doi: 10.3866/PKU.WHXB20101005

• QUANTUM CHEMISTRY AND COMPUTATION CHEMISTRY • Previous Articles     Next Articles

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

ZHONG Ai-Guo1, HUANG Ling1, LI Bai-Ling1, JIANG Hua-Jiang1, LIU Shu-Bin2   

  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:2010-06-10 Revised:2010-07-16 Published:2010-09-27
  • Contact: ZHONG Ai-Guo, LIU Shu-Bin E-mail:longlinyun@tzc.edu.cn;shubin@email.unc.edu

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Abstract:

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.

Key words: Electron