The bis- and tris-lut-substituted complexes, trans- and cis- 2– and mer- −, were synthesized by the reaction of 3– with an excess amount of lut in refluxed N, N-dimethylformamide. Photoirradiation of 4– with an excess amount of L afforded a mono-L-substituted hexanuclear rhenium(III) complex, 3– (L = 4-dimethylaminopyridine (dmap), 3,5-lutidine (lut), 4-methylpyridine (mpy), pyridine (py), 4,4′-bipyridine (bpy), 4-cyanopyridine (cpy), and pyrazine (pz)). The present study reports that the ground- and excited-state Re 6(23e)/Re 6(24e) redox potentials of an octahedral hexanuclear rhenium(III) complex can be controlled by systematically changing the number and type of the N-heteroaromatic ligand (L) and the number of chloride ions at the six terminal positions.
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