Computational study of topological effects on intramolecular electron transfer in mixed-valence compounds

doi:10.1007/s11458-011-0257-2

Front Chem Chin

2011, Vol. 6

Issue (4) : 280-286 https://doi.org/10.1007/s11458-011-0257-2

RESEARCH ARTICLE

Computational study of topological effects on intramolecular electron transfer in mixed-valence compounds

Yinxi YU, Haobin WANG(

)

Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces 88003, USA

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Abstract

The constrained density functional theory (CDFT) was used to investigate the topological effects on intramolecular electron transfer processes that have been reported in previous experimental work [Inorg. Chem., 1997, 36 (22), pp 5037-5049]. The computation mainly focused on three isomers of diferrocenylbenzenes (ortho, para, and meta) and 5-substituted derivatives of m-diferrocencylbenzenes with R= NH₂, Cl, CH₃, CN, NO₂, N(CH3)33+, and N2+. The influence of a third group R’ (R’ = NH₂ and N2+) was introduced to the ortho and para isomers. The calculations were compared with the experimental results. The relation between the substituted functional groups and the effectiveness of intramolecular electron transfer was discussed on the basis of CDFT computational results.

Corresponding Author(s): WANG Haobin,Email:haobin@nmsu.edu

Issue Date: 05 December 2011

Cite this article:

Yinxi YU,Haobin WANG. Computational study of topological effects on intramolecular electron transfer in mixed-valence compounds[J]. Front Chem Chin, 2011, 6(4): 280-286.

URL:

https://academic.hep.com.cn/fcc/EN/10.1007/s11458-011-0257-2
https://academic.hep.com.cn/fcc/EN/Y2011/V6/I4/280

Fig.1 Scheme 1 1o 1p 1m 2 3 4 5 6 7 8

Fig.2 Selected optimized molecular structures.(a) Molecular structure of 1o in Scheme 1;(b) Molecular structure of 3 in Scheme 1; (c) Molecular structure of 5 in Scheme 1

Tab.1 Selected bond lengths and torsion angles

Tab.2 Experimental and theoretical couplings (eV) for three isomers

Tab.3 Experimental and theoretical couplings (eV) for 1m family

Fig.3 Scheme 2 1o(1) 1o(2) 1o(3) 1o(4) 1p(1) 1p(2)

Tab.4 Experimental and theoretical couplings (eV) for three isomers and their derivatives

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