Acene Size-Dependent Transition of The Radical Centers From the Metal to The Acene Parts In Monocationic Dinuclear (Diethynylacene)diyl Complexes.

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, Me 3 Si-(C≡C) 2 -Ru(dppe) 2 -C≡C-Ar-C≡C-Ru(dppe) 2 -(C≡C) 2 -SiMe 3 (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.