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Issue 33, 2019
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Paddlewheel-type diruthenium(iii,iii) tetrakis(2-aminopyridinate) complexes with NIR absorption features: combined experimental and theoretical study

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Abstract

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 Ru26+ and triplet states, respectively. Cyclic voltammetry showed that 1 and 2 underwent one-electron 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 (δ*(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 π(amp or ammp) → δ*(Ru2) transition characteristics.

Graphical abstract: Paddlewheel-type diruthenium(iii,iii) tetrakis(2-aminopyridinate) complexes with NIR absorption features: combined experimental and theoretical study

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Publication details

The article was received on 29 May 2019, accepted on 22 Jun 2019 and first published on 24 Jun 2019


Article type: Paper
DOI: 10.1039/C9DT02271F
Dalton Trans., 2019,48, 12421-12429

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    Paddlewheel-type diruthenium(III,III) tetrakis(2-aminopyridinate) complexes with NIR absorption features: combined experimental and theoretical study

    Y. Kataoka, N. Imasaki, K. Arakawa, N. Yano, H. Sakiyama, T. Sugimori, M. Mitsumi and M. Handa, Dalton Trans., 2019, 48, 12421
    DOI: 10.1039/C9DT02271F

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