Abstract
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.
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Acknowledgements
This work was supported by JSPS KAKENHI Grant no. JP16H06514 (Coordination Asymmetry) and the special research grant from University of Hyogo (2016, 2017). Prof. Morifumi Fujita (University of Hyogo) is acknowledged for useful discussion on 1H NMR spectroscopy.
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This paper is dedicated to Professor Milan Melník for his outstanding contribution to coordination and bioinorganic chemistry.
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Ozawa, Y., Mori, M., Kiyooka, H. et al. Tetra- and hexanuclear copper(I) iminothiolate complexes: synthesis, structures, and solid-state thermochromic dual emission in visible and near-infrared regions. Chem. Pap. 74, 3717–3725 (2020). https://doi.org/10.1007/s11696-020-01251-w
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DOI: https://doi.org/10.1007/s11696-020-01251-w