金属串配合物(n, m)[Cr3(PhPyF)4Cl2](n=2, 3, 4; m=2, 1, 0)的配位结构及其与电场的关系

doi:10.3866/PKU.WHXB201505143

Acta Phys. -Chim. Sin. ›› 2015, Vol. 31 ›› Issue (7): 1323-1330.doi: 10.3866/PKU.WHXB201505143

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Coordination Structures of Metal String Complexes (n, m)[Cr₃(PhPyF)₄Cl₂](n=2, 3, 4; m=2, 1, 0) and Relationship with External Electric Field

DING Dan-Dan¹, XU Xuan^1,2,3,4,5, WU Zi-Wen¹, ZHOU Wo-Hua¹, CHEN Rong¹, XU Zhi-Guang^1,2,5

1 School of Chemistry & Environment, South China Normal University, Guangzhou 510006, P. R. China;
2 Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, Guangzhou 510006, P. R. China;
3 Key Laboratory of Electrochemical Technology on Energy Storage and Power Generation in Guangdong Universities, Guangzhou 510006, P. R. China;
4 Engineering Research Center of Materials and Technology for Electrochemical Energy Storage, Ministry of Education of China, Guangzhou 510006, P. R. China;
5 Key Laboratory of Materials for Energy Conversion and Storage of Guangzhou, Guangzhou 510006, P. R. China

Received:2015-03-19 Revised:2015-05-14 Published:2015-07-08
Contact: XU Xuan E-mail:xuxuan@scnu.edu.cn
Supported by:
The project was supported by the Natural Science Foundation of Guangdong Province, China (S2012010008763), Ministry of Education Research Project of Guangdong Province, China (2010B090400184), Science and Technology Program of Guangzhou City, China (2011J4300063).

Abstract

Abstract:

The coordination structures of metal string complexes (n, m)[Cr₃(PhPyF)₄Cl₂] (HPhPyF=N, N'- phenylpyridylformamidine; n=2, 3, 4; m=2, 1, 0) with potential applications as molecular wires have been investigated using the density functional theory BP86 method by considering the effects of an external electric field (EF). Herein, n and m represent the number of benzene rings on the left and right in the PhPyF- ligand, respectively. The results show that: (1) under zero field, the three kinds of coordination modes ((2, 2), (3, 1), (4, 0)) of the four PhPyF- ligands are close in energy, which indicates that they are competitive conformations. The (2, 2) coordination mode is the most stable one. The Cl axial ligands on the two sides of (4, 0) can coordinate to Cr atoms, indicating that these two axial ligands can combine with electrodes. Moreover, the Cl₄― Cr1 bond is stronger than Cl5―Cr3, different from (4, 0) [CuCuM(npa)₄Cl] [PF₆] (M=Pd, Pt; 2- naphthyridylphenylamine) in which the axial ligand Cl close to benzene cannot coordinate to metal atom M. (2) There is a 3-center-3-electron delocalization σ bond in the Cr₃^{6 +} chain for (2, 2), (3, 1), and (4, 0), but the delocalization gradually weakens. The polarity from Cl₄ to Cl5 is stronger as the coordination mode of four PhPyF- ligands becomes more consistent. (3) The geometry and electronic structure of the investigated complexes change regularly under the electric field. Because the electron transfer direction of (3, 1) and (4, 0) is the same as its molecular polarity, the bond length, spin density, charge and energy gap are more sensitive to -Z electric field. Therefore, the -Z elelctric field is beneficial to the conductivity of the molecules. Moreover, the sensitivity of the structures to electric field increases with polarity.

Key words: Metal string complex, Density functional theory, Coordination mode, Electric field, Molecular polarity

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DING Dan-Dan, XU Xuan, WU Zi-Wen, ZHOU Wo-Hua, CHEN Rong, XU Zhi-Guang. Coordination Structures of Metal String Complexes (n, m)[Cr₃(PhPyF)₄Cl₂](n=2, 3, 4; m=2, 1, 0) and Relationship with External Electric Field[J]. Acta Phys. -Chim. Sin. 2015, 31(7), 1323-1330. doi: 10.3866/PKU.WHXB201505143

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Coordination Structures of Metal String Complexes (n, m)[Cr₃(PhPyF)₄Cl₂](n=2, 3, 4; m=2, 1, 0) and Relationship with External Electric Field

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Coordination Structures of Metal String Complexes (n, m)[Cr3(PhPyF)4Cl2](n=2, 3, 4; m=2, 1, 0) and Relationship with External Electric Field

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Coordination Structures of Metal String Complexes (n, m)[Cr₃(PhPyF)₄Cl₂](n=2, 3, 4; m=2, 1, 0) and Relationship with External Electric Field