3 years ago

Manipulation and Assessment of Charge and Spin Delocalization in Mixed-Valent Triarylamine–Vinylruthenium Conjugates

Manipulation and Assessment of Charge and Spin Delocalization in Mixed-Valent Triarylamine–Vinylruthenium Conjugates
Rainer F. Winter, Christopher Hassenrück
Judicious choice of the aryl substituents R at the amine site of triarylamine−vinylruthenium conjugates (4-RC6H4)2N{C6H4-4-CH═CHRu(CO)Cl(PiPr3)2} controls the mutual contributions of the vinylruthenium and triarylamine redox sites to the relevant frontier molecular orbitals and the charge and spin densities at each of these sites in the corresponding mixed-valent radical cations. The latter remain electronically strongly coupled, as indicated by IR, electron paramagnetic resonance, and UV/vis/near-infrared spectroscopy and the skewing and nonsolvatochromic behavior of the intervalence charge-transfer band.

Publisher URL: http://dx.doi.org/10.1021/acs.inorgchem.7b02186

DOI: 10.1021/acs.inorgchem.7b02186

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