4.4 Article Proceedings Paper

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

Journal

CHEMICAL PAPERS
Volume 74, Issue 11, Pages 3717-3725

Publisher

SPRINGER INTERNATIONAL PUBLISHING AG
DOI: 10.1007/s11696-020-01251-w

Keywords

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

Funding

  1. JSPS KAKENHI [JP16H06514]
  2. University of Hyogo

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Two new photoluminescent multinuclear Cu(I) cluster complexes supported by monoanionic bidentate ligandN-methylbenzimidazolethiolate (Me-bimt(-)), [Cu-n(Me-bimt)(n)] withn = 4 (1) and 6 (2), have been synthesized and structurally characterized by single-crystal X-ray diffraction analysis. For1and2, 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, complexes1and2exhibit green (lambda(em) = 500 nm) and near-infrared (lambda(em) = 876 nm) emission, respectively, under UV irradiation (lambda(ex) = 365 nm) at room temperature. Both crystals reveal temperature-dependent dual emission below 200 K: complex1emits in the visible wavelength region (lambda(em) = 493 and 542 nm) and complex2in the visible to near-infrared wavelength region (lambda(em) = 752 and 973 nm) which are attributed to multiple photoexcited states at the cluster frameworks with distinct metal nuclearity.

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