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- Title
A Diruthenium‐Based Mixed Spin Complex Ru<sub>2</sub><sup>5+</sup>(S=1/2)‐CN‐Ru<sub>2</sub><sup>5+</sup>(S=3/2).
- Authors
Su, Shao‐Dong; Zhu, Xiao‐Quan; Wen, Yue‐Hong; Zhang, Lin‐Tao; Yang, Yu‐Ying; Lin, Chen‐Sheng; Wu, Xin‐Tao; Sheng, Tian‐Lu
- Abstract
An unusual tetra‐nuclear linear cyanido‐bridged complex [Ru2(μ‐ap)4‐CN‐Ru2(μ‐ap)4](BPh4) (1) (ap=2‐anilinopyridinate) has been synthesized and well characterized. The crystallographic data, magnetic measurement, IR, EPR and theoretical calculation results demonstrate that complex 1 is the first example of mixed spin Ru25+‐based complex with uncommon electronic configurations of S=1/2 for the cyanido‐C bound Ru25+ and S=3/2 for the cyanido‐N bound Ru25+. This phenomenon can be understood by the theoretical calculation results that from the precursor Ru2(μ‐ap)4(CN) (S=3/2) to complex 1 the energy gap between π* and δ* orbitals of the cyanido‐C bound Ru25+ core increases from 0.57 to 1.61 eV due to the enhancement of asymmetrical π back‐bonding effect, but that of the cyanido‐N bound Ru25+ core is essential identical (0.56 eV). Besides, the analysis of UV/Vis‐NIR spectra suggests that there exists metal to metal charge transfer (MMCT) from the cyanido‐N bound Ru25+ (S=3/2) to the cyanido‐C bound Ru25+ (S=1/2), supported by the TDDFT calculations.
- Subjects
ELECTRON configuration; BAND gaps; CHARGE transfer; MAGNETIC measurements; SPECTRUM analysis
- Publication
Angewandte Chemie, 2019, Vol 131, Issue 43, p15488
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201909097