Notable differences between oxidized diruthenium complexes bridged by four isomeric diethynyl benzodithiophene...

Four new diruthenium complexes [{(η(5)-C5Me5)Ru(dppe)}2(μ-C[triple bond, length as m-dash]C-L-C[triple bond, length as m-dash]C)] featuring different bridging isomeric diethynyl benzodithiophenes viz. L = benzo[1,2-b;4,5-b']dithiophene (complex ), benzo[2,1-b;4,5-b']dithiophene (complex ), benzo[1,2-b;3,4-b']dithiophene (complex ) and benzo[1,2-b;4,3-b']dithiophene (complex ), were synthesized and characterized by molecular spectroscopic and crystallographic methods. The subtle changes in the molecular structure introduced by the diethynyl benzodithiophene isomers have a notable impact on the stability of the oxidized complexes and their absorption characteristics in the visible-NIR and IR spectral domains. Electronic properties of stable oxidized complexes [](n+) and [](n+) (n = 1, 2) were investigated by cyclic voltammetry, UV-vis-NIR and IR spectroelectrochemistry as well as DFT and TDDFT calculations. The results document the largely bridge-localized character of the oxidation of parents and . Cations [](+) and [](+) are too unstable at ambient temperature to afford their unambiguous characterization. UV-vis-NIR absorption spectral data combined with TDDFT calculations (BLYP35) reveal that the broad electronic absorption of [](+) and [](+) in the NIR region has a mixed intraligand π-π* and MLCT character, with similar contribution from their spin-delocalized trans and cis conformers. A spin-localized (mixed-valence) rotamer was only observed for [](+) at ambient temperature as a minor component on the time scale of IR spectroscopy.