Issue 11, 2023

An ultra-stable Cu I12 cluster built from a Cu I6 precursor sandwiched by two Cu I3-thiacalixarene units for efficient photothermal conversion

Abstract

We report the synthesis, crystal structure, optical properties, and photothermal conversion properties of an ultra-stable cuprous Cu12 cluster, namely {[CuI3(HTC4A)]2[CuI6(2-PyS)6]}·H2O (Cu12, H4TC4A = p-tert-butylthiacalix[4]arene, 2-PySH = 2-pyridinethiol), which was built from a pre-synthesized CuI6(2-PyS)6 (Cu6) precursor and two CuI3-HTC4A polynuclear secondary building units (PSBUs). The Cu12 cluster features a sandwich-like framework in which the Cu6 core is double surface capped by forming six Cu–S bonds with two CuI3-HTC4A PSBUs. The “cluster–cluster” assembly strategy enables all the metal centers in the Cu12 cluster to be monovalent and efficient organic ligand protection makes the cuprous cluster stable in common solvents (alcohol, acetonitrile, acetone, CHCl3, N N-dimethylacetamide, etc.) as well as in strong acids (pH = 1) or bases (pH = 14). Band gap determination and photophysical analysis combined with density functional theory (DFT) calculations indicated that CuI3-HTC4A PSBUs can tune the electron and hole distribution of the Cu6 core, which makes Cu12 a stable and efficient photothermal conversion material both in the solid state and in water/N,N-dimethylformamide solvents.

Graphical abstract: An ultra-stable CuI12 cluster built from a CuI6 precursor sandwiched by two CuI3-thiacalixarene units for efficient photothermal conversion

Supplementary files

Article information

Article type
Research Article
Submitted
15 Mar 2023
Accepted
24 Apr 2023
First published
25 Apr 2023

Inorg. Chem. Front., 2023,10, 3230-3236

An ultra-stable CuI12 cluster built from a CuI6 precursor sandwiched by two CuI3-thiacalixarene units for efficient photothermal conversion

Z. Zhou, L. Xu, G. Zhao, K. Zhou, B. Chen and Y. Bi, Inorg. Chem. Front., 2023, 10, 3230 DOI: 10.1039/D3QI00479A

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