2019年9月
Paddlewheel-type diruthenium(III, III) tetrakis(2-aminopyridinate) complexes with NIR absorption features: combined experimental and theoretical study
DALTON TRANSACTIONS
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- 巻
- 48
- 号
- 33
- 開始ページ
- 12421
- 終了ページ
- 12429
- 記述言語
- 英語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1039/c9dt02271f
- 出版者・発行元
- ROYAL SOC CHEMISTRY
The reactions of [ Ru2(O2CCH3) 4Cl] with 2-aminopyridine (Hamp) and 2-amino-4-methylpyridine (Hammp) afforded two novel Ru2 complexes, [ Ru2(amp) 4Cl2] (1) and [ Ru2(ammp) 4Cl2] (2), respectively. Single crystal X-ray diffraction analyses revealed that 1 and 2 adopted typical paddlewheel-type structures, where the Ru2 units are coordinated with four aminopyridinate ligands with a cis-2: 2 arrangement at the equatorial positions and two chloride ligands at the axial positions. The stabilities of 1 and 2 were supported by unrestricted density functional theory (uDFT) calculations. The zero-point energies of the three structural isomers (trans-2: 2, 3: 1, and 4: 0 arrangements) of 1 and 2 were less stable than those of the respective cis-2: 2 arrangements. Temperature-dependences of the magnetic susceptibility measurements and uDFT calculations showed that the oxidation and spin states of the Ru2 units in 1 and 2 were commonly Ru2 6+ and triplet states, respectively. Cyclic voltammetry showed that 1 and 2 underwent oneelectron reduction processes, i. e., 1/1-and 2/2-, at redox potentials (E1/2) of -0.08 and -0.18 V vs. SCE, respectively. These results agreed well with the DFT-calculated E1/2 values of 1 (-0.08 V vs. SCE) and 2 (-0.18 V vs. SCE) and were theoretically attributed to Ru2-centred (d*(Ru2)) redoxes. Moreover, 1 and 2 showed unique near-infrared absorption bands at approximately 1200-1500 nm, which were theoretically attributed to the ligand-to-metal charge transfer (LMCT) with p(amp or ammp). d*(Ru2) transition characteristics.
- リンク情報
- ID情報
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- DOI : 10.1039/c9dt02271f
- ISSN : 1477-9226
- eISSN : 1477-9234
- Web of Science ID : WOS:000481917100039