THEORETICAL AND SPECTROSCOPIC INVESTIGATIONS OF METAL-ORGANIC ION-PAIRS WITH DITHIOLENE OR DITHIOOXALATE DONOR COMPLEXES AND VIOLOGENS

Bipyridinium and phenanthrolinium accepters (A(2+)) Of different reduc tion potentials and (dithiooxalato) metalates form ion-pair charge-tra nsfer complexes of the general formula {A[M(dto)(2)]}, where M=Ni, Pd, Pt, Cu, Zn, and dto = 1,2-dithiooxalate. Compared with analogous ion pairs consisting of a dithiolene donor component the hypsochromic shif t of the ion-pair charge-transfer (IPCT) band, which is a characterist ic feature of the systems is discussed. The particular orbital structu re of the highest occupied MO influences significantly the electrochem ical and photochemical properties of both groups of metal-organic ion pairs.