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Updated: May 10, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Protonation-Induced Reversible Switching of Electronic Delocalization in a Linear Ru-Ru-Ru Complex
Jin-Hui Fu1,2, Zi-Hang Wu1,2, Ying Song1,2
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.
Abstract:
In this work, we report the first example of a molecular switch between electronic delocalization and electronic localization in cyanidometal-bridged trinuclear mixed-valence (MV) complex controlled by a protonation reaction. A MV complex with the terminal 2,3-bis(diphenylphosphino)pyridine (L) ligand which has a higher proton-accepting character, LRuIII-NC-RuII-CN-RuIIL (13+) was synthesized and well characterized. The investigations indicate that the interaction between the two terminal Ru centers of 13+ is so strong that it is fully delocalized and can be described as LRuII+0.5-NC-RuII-CN-RuII+0.5L. Most interestingly, 13+ can be reversibly protonated to 13+-2H coupled with an electron transfer from the central RuII to the terminal RuIII, resulting in a change in electronic structure from LRuII+0.5-NC-RuII-CN-RuII+0.5L to HLRuII-NC-RuIII-CN-RuIILH. Cyclic voltammogram of 13+-2H showed very weak interaction between the two terminal Ru centers. The remarkable change in electronic states by protonation-induced electron transfer is also strongly supported by the (TD)DFT calculations. Complex 13+ may be potential for an excellent candidate of molecular switch.
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