Different manifestations of enhanced p-acceptor ligation at every redox level of Os(9-OP)L2n, n = 2+, +, 0, - (9-OP- = 9-oxidophenalenone and L = bpy or pap)
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Dalton Transactions 45 (45): 18241--18251 (2016)

The title complexes were isolated as structurally characterized compds. OsII(9-OP)L2ClO4, L = 2,2'-bipyridine (bpy) or 2-phenylazopyridine (pap), and were compared with ruthenium analogs. A reversible one-electron oxidn. and up to three redn. processes were obsd. by voltammetry (CV, DPV) and spectroelectrochem. (UV-vis-NIR, partially EPR). Supporting calcns. (DFT, TD-DFT) were used to assess the oxidn. state combinations of the different redox active ligands and of the metal, revealing the effects of Os vs. Ru exchange and of bpy vs. pap acceptor ligation. Several unexpected consequences of these variations were obsd. for members of the new osmium-contg. redox series. Remarkably, the EPR results exhibit a clear dichotomy between the complex ion OsIII(9-OP-)(bpy)22+ and the radical species OsII(9-OP)̇(pap)22+, which has not been similarly obsd. for the analogous RuIII(9-OP-)L22+ systems. This difference, unprecedented for 5dn systems, is attributed to the superior stabilization of the OsII state by the strongly p-accepting pap ligands. The reduced forms OsII(9-OP-)(pap ̇-)(pap) and OsII(9-OP-)(pap ̇-)2- exhibit strong inter-ligand interactions, leading to spin isomers and electron hopping. on SciFinder(R)
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