《Role of Substituents at 3-position of Thienylethynyl Spacer on Electronic Properties in Diruthenium(II) Organometallic Wire-like Complexes》 was written by Roy, Sourav Saha; Chowdhury, Sabyasachi Roy; Mishra, Sabyashachi; Patra, Sanjib K.. Synthetic Route of C4H2Br2S And the article was included in Chemistry – An Asian Journal in 2020. The article conveys some information:
Organometallic complexes [Cl(dppe)2Ru-C C-(3-R-C4H2S)-C C-Ru(dppe)2Cl] (3-R-C4H2S = 3-substituted thienyl moiety; R = -H, -C2H5, -Pr, -Bu, -C6H13, -OMe, -CN in 5a-5g, resp.) were synthesized by systematic variation of 3-substituents at the thienylethynyl bridging unit. The diruthenium(II) wire-like complexes (5a-5g) were achieved by the reaction of thienylethynyl bridging units, Hc C-(3-R-C4H2S)-C CH (4 a-4 g) with cis-[Ru(dppe)2Cl2]. The wire-like diruthenium(II) complexes undergo two consecutive electrochem. oxidation processes in the potential range of 0.0-0.8 V. 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, d. functional theory (DFT) calculations of the selected diruthenium wire-like complexes (5a-5e) with different alkyl appendages were performed. The theor. data demonstrate that incorporation of alkyl groups to the thienylethynyl entity leaves unsym. spin densities, thus affecting the electronic properties. The voltammetric features of the other two Ru(II) alkynyl complexes 5f and 5g (with -OMe and -CN group, resp.) show an apparent dependence on the electronic properties. The electronic properties in the redox conjugate, (5a+) with Kc of 3.9 × 106 are further examined by UV-visible-NIR and FTIR studies, showing optical responses in NIR region along with changes in -Ru-C C- vibrational stretching frequency. The origin of the observed electronic transition was assigned based on time-dependent DFT (TDDFT) calculations In the part of experimental materials, we found many familiar compounds, such as 2,5-Dibromothiophene(cas: 3141-27-3Synthetic Route of C4H2Br2S)
2,5-Dibromothiophene(cas: 3141-27-3) , is mainly used as pharmaceutical intermediate and synthesis intermediate. 2,5-Dibromothiophene may be used as starting reagent for the synthesis of α,α′-didecylquater-, -quinque- and -sexi-thiophenes.Synthetic Route of C4H2Br2S
Referemce:
Bromide – Wikipedia,
bromide – Wiktionary