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Photophysical property of $$catena$$-bis(thiocyanato)aurate(I) complexes in ionic liquids

擬一次元金(I)ビスチオシアナト錯体のイオン液体中における光物性

青柳 登; 榛葉 祐介*; 池田 篤史*; 芳賀 芳範; 下条 晃司郎; Brooks, N. R.*; 泉岡 明*; 長縄 弘親; 木村 貴海; Binnemans, K.*

Aoyagi, Noboru; Shinha, Yusuke*; Ikeda, Atsushi*; Haga, Yoshinori; Shimojo, Kojiro; Brooks, N. R.*; Izuoka, Akira*; Naganawa, Hirochika; Kimura, Takaumi; Binnemans, K.*

金(I)チオシアナト錯体の光化学を研究し、固体および液体中における配位構造を決定した。この超分子錯体と光励起状態における励起錯体の配位構造を、単結晶構造解析および放射光XASによって解析した。基底状態と光励起状態におけるAu-SおよびAu-Auの結合距離を比較した。紫外光の照射に伴って、励起錯体の相互作用は強まり、Au-Au間の距離が縮まった。1次元鎖からはブロードな発光スペクトルが観測された。時間分解発光スペクトルは、凝集形態の異なるオリゴマーの存在を示した。さらに、EXAFSは光刺激によってAu-Sの距離が変化することを示した。光励起錯体の歪みは液体では有意に観測されなかった。これは、錯体のフレキシブルな構造が原因である思われる。結果として、擬1次元構造をもつ錯体は、光励起によって超分子ネットワークの結合距離を制御できることが分かった。

The photochemistry of a gold(I) thiocyanate complex has been investigated to determine the coordination structure in both the solid and liquid states. The coordination geometries of the supramolecular complex and the concomitant exciplex have mainly been analyzed by crystallographic analysis and X-ray absorption spectroscopy. The Au-S bond distance and Au-Au separation of the compound in the ground state and in the phosphorescent excited state were compared. Upon irradiation with UV light, the excimeric interactions were enhanced, resulting in a contraction of the Au-Au aurophilic distance. A broad luminescence spectrum was observed for the one-dimensional chain suprastructure. The time-resolved luminescence spectra indicated the entity of several oligomeric species in the crude liquid without neutral solvent molecules. In addition, EXAFS spectroscopy exhibited a slight change in the nearest Au-S distance due to the photo-switched transformation. The deformation of the (Au-Au)* exciplexes was not apparently promoted in the liquid state with the asymmetrical imidazoium cations having a non-local charge distribution in the present observation. This is plausibly due to a flexible molecular structure and a property in the liquid state. In conclusion, the photo-excited nature of the pseudo-one dimensional complexes is emerged in controlling bond distances among the supramolecular networks.

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パーセンタイル:31.11

分野:Chemistry, Multidisciplinary

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