Rhenium(I) Tricarbonyl Complexes with Peripheral N-Coordination Sites: A Foundation for Heterotrimetallic Nonlinear Optical Chromophores

The compounds 4,4′-dicyano-2,2′-bipyridyl (dcbpy), 4,4′-bis(4-cyanophenyl)-2,2′-bipyridyl (bcpbpy), 4,4′-bis[(E)-2-(4-cyanophenyl)vinyl]-2,2′-bipyridyl (bcpvbpy), and 4,4′-bis[(E)-2-(4-pyridyl)vinyl]-2,2′-bipyridyl (bpvbpy) are used to prepare nine new complexes with fac-{ReI(CO)3(L)}n+ (L = Cl–, MeCN, pyridine (py), or 4-cyanopyridine (cpy)) centers. The cationic complexes are isolated as their OTf– salts. These new monometallic species are studied together with the known fac-ReICl(CO)3(qpy) (qpy = 4,4′:2′,2″:4″,4‴-quaterpyridyl) (de Wolf, P.; et al. Inorg. Chim. Acta 2003, 355, 280–285). Coordination of {RuII(NH3)5}2+ centers to the peripheral N atoms of fac-ReICl(CO)3(qpy) and fac-[ReI(CO)3(bcpbpy)(py)]+ affords heterotrimetallic complexes that are isolated as their PF6– salts. Single-crystal X-ray structures are reported for the solvates fac-ReICl(CO)3(dcbpy)·Me2CO, fac-[ReI(CO)3(dcbpy)(MeCN)]OTf·PhMe, fac-[ReI(CO)3(dcbpy)(py)]OTf·0.5PhMe, fac-[ReI(CO)3(dcbpy)(cpy)]OTf·0.5Me2CO, fac-ReICl(CO)3(bcpbpy)...