The preparation, structures and spectroscopic properties of binuclear rhodium complexes and [platinum(phosphorus hydrogen oxygen)]/viologen systems: Time-resolved photocrystallography and the study of photoinduced intermolecular electron transfer
Gerlits, Oksana O
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Several transition metal complexes of Rh(I), which have different bridging ligands, and the Ru(II) compound, being potential candidates for the time-resolved diffraction studies have been synthesized. Various counterions, including [PF 6 ] - , [BPh 4 ] - and [calyxarene-H] - were used, the latter is necessary to reduce the cation concentration in the solid state. Their low-temperature crystal structures, very low temperature solid-state emission and room temperature solid-state absorption spectra have been studied. Several donor-acceptor crystals of Ptpop as an electron donor and MV, PV and BV as electron acceptors were prepared. The combined crystallographic studies, solid-state emission, absorption and EPR spectra have been done in order to study the structural and spectroscopic properties of such charge transfer systems in the crystalline medium. The experiments are supported by the theoretical calculations of the three viologen molecules in the dication and cation radical states. Time-resolved photocrystallographic experiments were carried out for the [Rh 2 (dimen) 4 ][PF 6 ] 2 , [Rh 2 PNP 4 ][BPh 4 ] 2 and K 2 MV[Pt 2 (pop) 4 ] compounds. In all the experiments the shortening of a M-M bond was observed, the magnitude being dependent on the ground state M-M distance and the nature of the complex.