Bis-triarylamine with a cyclometalated diosmium bridge: A multi-stage redox-active system |
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Authors: | Meng-Jia Sun Hai-Jing Nie Jian-Nian Yao Yu-Wu Zhong |
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Institution: | Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, ;
Beijing 100190, China |
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Abstract: | A tetra(pyrid-2-yl)-pyrazine-bridged cyclometalated diosmium complex 1(PF6)2 with two distal redoxactive organic amine substituents has been synthesized and characterized. This complex displays four consecutive and separated anodic redox waves at +0.24, +0.38, +0.64, and +0.71 V vs. Ag/AgCl. Upon stepwise oxidation, four-step absorption spectral changes in the visible to near-infrared region have been observed. The different redox states of 1 (12+ through 16+) can be distinguished by the significantly different absorption spectra in the visible and near-infrared region. DFT calculations of 13+ show that the spin is delocalized on both osmium-amine components. |
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Keywords: | Mixed-valent compounds Spectroelectrochemistry Near-infrared electrochromism Redox-active compounds Triarylamines |
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