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
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