Abstract
Synthesis and structural characterization of a family of germanium-dioxolene complexes with ditopic N-donor ligands (L1-L5) (L1 = 1,2-bis(pyridin-2-ylmethylene)hydrazine L2 = 1,6-bis-(pyridin-2-yl)-2,5-diaza-1,5-heхаdiene, L3 = N,N-bis(pyridin-2-ylmethylene)-1,4-benzenediamine, L4 = N,N-bis(pyridin-2-ylmethylene)-(biphenyl)-4,4-diamine, L5 = 2,2'-azopyridine) is reported. The reaction of germanium bis-catecholate with bridging ligands L1 - L4, differing by the nature of the linker between pyridine sites gives rise to dinuclear digermanium complexes (36Cat2Ge)2L1-4 (36Cat = dianion of 3,6-di-tert-butylcatechol) 1-4 of DMAMD type (donor-metal-acceptor-metal-donor) with a charge transfer in the UV-Vis region. In opposite, the interaction of the 36Cat2Ge with 2,2'-azopyridine (L5) results in the two-electron transfer from the donor 36Cat2- ligands to the azopyridine bridge forming stable open-shell complex 5 [(36SQ)(36CatGe)]2(L5)2- (36SQ = radical-anionic semiquinonate ligand). Molecular structures of compounds 3 and 5 were determined by single crystal X-ray diffraction analysis. Electronic structures of complexes 1-5 were studied by means of DFT calculations.
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