Ground and excited state properties of the newly prepared complexes Re(CO) 3 (2,2′-biquinoline)L S + , L S ) pyrazine or 4,4′-bipyridine, and Re(CO) 3 (2,2′-bipy)(2-pyrazinecarboxylate) were investigated by steady state and time-resolved spectroscopy. The X-ray structure of the latter compound showed that the spectator ligand 2-pyrazinecarboxylate is coordinated through the carboxylate group to Re(I). A component of the complexes' luminescence was associated with long-lived Re to ligand, 2,2′-biquinoline or 2,2′-bipy, charge transfer, while a fast component of the emission was associated with intraligand excited states. Quenching of the luminescence by CuCl 2 involved energy transfer via dynamic and static mechanisms. The complexes in their excited states were reduced by 2,2′,2′′-nitrilotriethanol with the formation of Re(I) ligand-radical species. Similar products were generated by the pulse radiolytic reduction of the complexes. The photochemical properties of the 2,2′-biquinoline complexes and Re(CO) 3 (1,10-phen)4-nitrobenzoate are compared, and the mechanisms of their photochemical reactions are discussed.
Several BrRe(CO)3L complexes (where L groups are 2,2'-biquinoline substituted in the 3 and 3' positions) were prepared. Their pseudooctahedralfuc structure was established by using FTIR, UV-vis, and 1H-NMR and confirmed by X-ray analysis. A good correlation between the electrochemical parameters and the MLCT electronic transition was found. The crystalline compound, BrRe(C0)3(3,3'-trimethylene-2,2'-biquinoline) belongs to triclinic space groupPiwitha=9,113(11)A,b= 10.192(4)A,c= 12.825(5)A,ar=73.23(4)0,B=81.30(7)0,andy=66.55(5)0.The volume of the unit cell is 1048(1) A3 with Z = 2. The structure was refined to R = 0.040.
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