Role of Substituents at 3-position of Thienylethynyl Spacer on Electronic Properties in Diruthenium(II) Organometallic Wire-like Complexes

A series of organometallic complexes [Cl(dppe)(2)Ru-C equivalent to C-(3-R-C4H2S)-C equivalent to C-Ru(dppe)(2)Cl] (3-R-C4H2S=3-substituted thienyl moiety; R=-H, -C2H5, -C3H7, -C4H9, -C6H13, -OMe, -CN in5 a-5 grespectively) have been synthesized by systematic variation of 3-substituents at the thienylethynyl bridging unit. The diruthenum(II) wire-like complexes (5 a-5 g) have been achieved by the reaction of thienylethynyl bridging units, HC equivalent to C-(3-R-C4H2S)-C equivalent to CH (4 a-4 g) withcis-[Ru(dppe)(2)Cl-2]. The wire-like diruthenium(II) complexes undergo two consecutive electrochemical oxidation processes in the potential range of 0.0 - 0.8 V. Interestingly, the wave separation between the two redox waves is greatly influenced by the substituents at the 3-position of the thienylethynyl. Thus, the substitution on 3-position of the thienylethynyl bridging unit plays a pivotal role for tuning the electronic properties. To understand the electronic behavior, density functional theory (DFT) calculations of the selected diruthenium wire-like complexes (5 a-5 e) with different alkyl appendages are performed. The theoretical data demonstrate that incorporation of alkyl groups to the thienylethynyl entity leaves unsymmetrical spin densities, thus affecting the electronic properties. The voltammetric features of the other two Ru(II) alkynyl complexes5 fand5 g(with -OMe and -CN group respectively) show an apparent dependence on the electronic properties. The electronic properties in the redox conjugate, (5 a(+)) with K(c)of 3.9x10(6)are further examined by UV-Vis-NIR and FTIR studies, showing optical responses in NIR region along with changes in -Ru-C equivalent to C- vibrational stretching frequency. The origin of the observed electronic transition has been assigned based on time-dependent DFT (TDDFT) calculations.