Acene Size-Dependent Transition of The Radical Centers From the Metal to The Acene Parts In Monocationic Dinuclear...

Controlling radical localization/delocalization is important for functional materials. The present paper describes synthesis and results of electrochemical, spectroscopic, and theoretical studies of diruthenium (p-diethynylacene)diyl complexes, Me₃ Si-(C≡C)₂ -Ru(dppe)₂ -C≡C-Ar-C≡C-Ru(dppe)₂ -(C≡C)₂ -SiMe₃ (1-6) (dppe: 1,2-bis(diphenylphosphino)ethane), and their monocationic radical species ([1]⁺ -[6]⁺ ). The HOMO-LUMO energy gaps can be finely tuned by the acene rings in the bridging ligands installed, as indicated by the absorption maxima of the electronic spectra of 1-6 ranging from the UV region even to the NIR region. The cationic species [1]⁺ -[6]⁺ show two characteristic NIR bands, which are ascribed to the charge resonance (CR) and π-π* transition bands, as revealed by spectroelectrochemistry. Expansion of the acene rings in [1]⁺ -[6]⁺ causes (1) blue shifts of the CR bands and red shifts of the π-π* transition bands and (2) charge localization on the acene parts as evidenced by the ESR, DFT and TD-DFT analyses. Notably, the monocationic complexes of the larger acene derivatives are characterized as the non-classical acene-localized radicals.