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Role of -Elements in a Proton-Electron Coupling of -π Hybridized Electron Systems.

著者 Hayashi M , Takahashi Y , Yoshida Y , Sugimoto K , Kitagawa H
J Am Chem Soc.2019 Jul 12 ; ():.
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We first demonstrate the influence of -elements on the electronic-state alternation of molecules coupled with proton transfer in -π hybridized electron systems. Compact and planar metal complexes with protonated 2,3-pyrazinedithiolates (), ( = Ni, Pd, and Pt), were synthesized and subsequently determined to be assembled by hydrogen bond (H-bond) interactions between pyrazine moieties. Structural and theoretical investigations revealed that these complexes are regarded as -π hybridized electron systems based on a M(SC) core, especially, significant -π hybridization in the Pt(SC) core was indicated. The pH-dependent optical and electrochemical measurements revealed that the Ni complex has a higher proton-accepting character and a stronger pH dependence for redox potential compared with the Pt complex. This indicates that the Ni complex has a larger amount of π-electron density on ligands than the Pt complex because the significant -π hybridization in the Pt complex could reduce the amount of π-electron reconstructed by attaching/detaching proton. Cyclic voltammetry of Ni and Pt complexes that form an H-bonded multimer showed a potential splitting at the first redox wave (Δ = 0.28 V for M = Ni and 0.17 V for M = Pt) corresponding to a mixed-valence state coupled with proton transfer. The Δ values indicate that the change in electronic states by proton transfer is remarkable in the Ni complex, but moderate in the Pt complex. These experimental results lead that the -element substitution plays a role in controlling the degree of proton-electron coupling in -π hybridized electron systems.
PMID: 31298533 [PubMed - as supplied by publisher]
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