The application potential of mixed valent complexes in information transferand optical devices has initiated the development of newer molecular frameworks with well defined electrochemical and optical features. In this context structural and electronic properties of (m-oxa)[RuIII(acac)2]2 (1 )(oxa2- = oxamidato(2-) and acac- = 2,4-pentanedionato) have been explored. The S = 1 ground state of 1  (?E(S=0-S=1)= 9120 cm-1) exhibits intramolecular/intermolecular antiferromagnetic spin-spin coupling. The molecular structure of 1  reveals a notable asymmetry within the bridging ligand. The stepwise facile electron-transfers generate paramagnetic mixed valent intermediates: RuIVRuIII (1 +) and RuIIIRuII (1 -) of similar thermodynamic stability. The spin density calculations establish little participation of the bridge in spin accommodation. Although only one broad NIR band (IVCT) is observed for the RuIIIRuII (4d5/4d6) system in 1 -,the unusual RuIVRuIII (4d4/4d5)form in 1+  shows extended absorbance over the UV-vis-NIR range due to the presence of multiple transitions.

Remarkable correspondence between d5d6 and d4d5 mixed valent states

245th National Meeting (2013)

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