Benzo[1,2-b;4,5-bʹ]dithiophene-bridged bimetal complexes with different redox-active terminals: Syntheses, characterization and charge delocalization studied by spectro-electrochemical and DFT methods
| Autor: | Ya-Ping Ou, Yu Jiangxi, Junhua Li, Shunlin Tang, Zhang Fuxing, Fang Hu, Kuang Daizhi |
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| Rok vydání: | 2017 |
| Předmět: |
010405 organic chemistry
Ligand Chemistry Organic Chemistry Analytical chemistry chemistry.chemical_element Electrolyte 010402 general chemistry Electrochemistry 01 natural sciences Biochemistry Redox 0104 chemical sciences Bimetal Ruthenium Inorganic Chemistry Metal Crystallography Delocalized electron visual_art Materials Chemistry visual_art.visual_art_medium Physical and Theoretical Chemistry |
| Zdroj: | Journal of Organometallic Chemistry. 843:66-74 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/j.jorganchem.2017.05.032 |
| Popis: | Benzo[1,2-b;4,5-bʹ]dithiophene have been used as bridge ligand to build up binuclear iron ethynylene complex 1 and ruthenuim vinylene complex 2, and their electronic and optical properties were investigated by electrochemistry, IR and UV–vis–NIR spectroelectrochemistry and theoretical calculations. These properties of two complexes 1 and 2, for comparison, of the previously reported ruthenium ethynylene complex 3 was analyzed. Complexes 1–3 exhibit obvious different redox characteristics. The highest anodic potentials and the largest ΔE value were found in ruthenium vinylene complex 2. IR spectroelcetrochemistry results show that two intense ν(C≡C) bands of monocation 1+ feature more larger ν(C≡C) separation (73 cm−1) than that of 3+ (36 cm−1), and ν(C≡O) band in 2 exhibit little changes upon electrolytic experiments. The NIR broad absorptions of different strength and energy were found in singly-oxidized 1+-3+, which may be assigned to MLCT and proved further by DFT-TDDFT calculations. Similar to 3+, different conformations from the relative position difference between metal terminal groups and bridge ligands may be attributable to broad NIR absorptions of 1+. |
| Databáze: | OpenAIRE |
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