Intervalence Transfer at the Localized-to-Delocalized, Mixed-Valence Transition in Osmium Polypyridyl Complexes

The mixed-valence complexes [(bpy)(2)(Cl)Os(III)(BL)Os(II)(Cl)(bpy)(2)](3+) and [(tpy)(bpy)Os(III)(BL)Os(II)(bpy)(tpy)](5+) (bpy is bipyridine; tpy is 2,2':6',2' '-terpyridine; BL is a bridging ligand, either 4,4'-bipyridine (4,4'-bpy) or pyrazine (pz)) have been prepared and studied by infrared and near-infrared measurements in different solvents. For BL = 4,4'-bpy, there is clear evidence for localized Os(II) and Os(III) oxidation states in the appearance of the expected two interconfigurational dpi --> dpi bands at Os(III) and additional, broad absorption features in the near-infrared arising from intervalence transfer (IT) transitions. For [(bpy)(2)(Cl)Os(pz)Os(Cl)(bpy)(2)](3+) and [(tpy)(bpy)Os(pz)Os(bpy)(tpy)](5+), unusually intense nu(pz) bands appear in the infrared at 1599 cm(-)(1) (epsilon = 2600 M(-)(1) cm(-)(1)) for the former and at 1594 cm(-)(1) (epsilon = 2020 M(-)(1) cm(-)(1)) for the latter. They provide an oxidation state marker and evidence for localized oxidation states. A series of bands appear in the near-infrared from 2500 to 8500 cm(-)(1) that can be assigned to a combination of interconfigurational dpi --> dpi and IT transitions. In CD(3)CN, in the mid-infrared, bands arising from nu(bpy) ring stretching modes from 1400 to 1500 cm(-)(1) are averaged for [(bpy)(2)(Cl)Os(pz)Os(Cl)(bpy)(2)](3+) or significantly perturbed for [(tpy)(bpy)Os(pz)Os(bpy)(tpy)](5+) compared to electronically isolated Os(II) and Os(III) complexes. The pyrazine-bridged complexes have properties that place them in a new class of mixed-valence molecules, Class II-III having properties associated with both Class II and Class III in the Robin and Day classification scheme. The characteristic features of this class are that oxidation states are localized because of vibrational coupling but that solvent orientational motions are uncoupled because of rapid intramolecular electron transfer.