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Tetra- and hexanuclear copper(I) iminothiolate complexes: synthesis, structures, and solid-state thermochromic dual emission in visible and near-infrared regions

Yoshiki Ozawa, Marino Mori, Hidetoshi Kiyooka, Yuumi Sugata, Toshikazu Ono, and Masaaki Abe

Graduate School of Material Science, University of Hyogo, Hyogo, Japan



Received: 13 February 2020  Accepted: 13 June 2020


Two new photoluminescent multinuclear Cu(I) cluster complexes supported by monoanionic bidentate ligand N-methylbenzimidazolethiolate (Me-bimt), [Cun(Me-bimt)n] with n = 4 (1) and 6 (2), have been synthesized and structurally characterized by single-crystal X-ray diffraction analysis. For 1 and 2, the Cu(I) ions and the Me-bimt ligands construct a cubane-type {Cu4S4} and a hexagonal-prism {Cu6S6} frameworks, respectively. In the crystalline state, complexes 1 and 2 exhibit green (λem = 500 nm) and near-infrared (λem = 876 nm) emission, respectively, under UV irradiation (λex = 365 nm) at room temperature. Both crystals reveal temperature-dependent dual emission below 200 K: complex 1 emits in the visible wavelength region (λem = 493 and 542 nm) and complex 2 in the visible to near-infrared wavelength region (λem = 752 and 973 nm) which are attributed to multiple photoexcited states at the cluster frameworks with distinct metal nuclearity.

Keywords: Copper(I); Cluster compounds; Crystal structure; Thermochromic dual emission; Near-infrared emission

Full paper is available at

DOI: 10.1007/s11696-020-01251-w


Chemical Papers 74 (11) 3717–3725 (2020)

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