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- Title
Distinguishing the Strength of Electronic Coupling for Mo<sub>2</sub>-Containing Mixed-Valence Compounds within the Class III Regime.
- Authors
Cheng, Tao; Tan, Ying Ning; Zhang, Yu; Zhang, Yu Yu; Meng, Miao; Lei, Hao; Chen, Lu; Liu, Chun Y.
- Abstract
Two, symmetrical, mixed-valence (MV), complex cations-{[Mo2(DAniF)3]2(μ-oxamidate)}+ ( 1+) and {Mo2(DAniF)3]2(μ-dithiooxamidate)}+ ( 2+; DAniF= N,N′-di( p-anisyl)formamidinate)-are significantly differentiated in terms of electronic coupling between the two [Mo2] units. For 1+ the intervalence (IV) charge-transfer band in the near-IR spectrum is truncated in half on the low-energy side as predicted for MV compounds at the Class II-III limit (2 Hab/ λ=1; for which Hab=electronic coupling matrix element and λ=reorganization energy). In contrast, the very strongly coupled analogue 2+, as indicated by 2 Hab/ λ=3.5 (> >1), exhibits a higher energy and more symmetrical IV band. As rare examples, this pair of MV species shows distinct optical behaviors for MV systems crossing the Class III region. Optical analysis and DFT calculations are carried out to elucidate the transformation from vibronic to electronic vertical transition.
- Subjects
MOLYBDENUM oxides; VALENCE bands; CATIONS; CHARGE transfer; FORMAMIDINES
- Publication
Chemistry - A European Journal, 2015, Vol 21, Issue 6, p2353
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201406196