We report the synthesis,crystal structure,optical properties,and photothermal conversion properties of an ultra-stable cuprous Cu_(12) cluster,namely{[Cu_(3)^(I)(HTC_(4)A)]_(2)[Cu_(6)^(I)(2-PyS)_(6)]}·H_(2)O(Cu_(...We report the synthesis,crystal structure,optical properties,and photothermal conversion properties of an ultra-stable cuprous Cu_(12) cluster,namely{[Cu_(3)^(I)(HTC_(4)A)]_(2)[Cu_(6)^(I)(2-PyS)_(6)]}·H_(2)O(Cu_(12),H_(4)TC_(4)A=p-tertbutylthiacalix[4]arene,2-PySH=2-pyridinethiol),which was built from a pre-synthesized Cu_(6)^(I)(2-PyS)_(6)(Cu_(6))precursor and two Cu_(3)^(I)-HTC_(4)A polynuclear secondary building units(PSBUs).The Cu_(12) cluster features a sandwich-like framework in which the Cu_(6) core is double surface capped by forming six Cu-S bonds with two Cu_(3)^(I)-HTC_(4)A PSBUs.The“cluster-cluster”assembly strategy enables all the metal centers in the Cu_(12) cluster to be monovalent and efficient organic ligand protection makes the cuprous cluster stable in common solvents(alcohol,acetonitrile,acetone,CHCl_(3),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 Cu_(3)^(I)-HTC_(4)A PSBUs can tune the electron and hole distribution of the Cu_(6) core,which makes Cu_(12) a stable and efficient photothermal conversion material both in the solid state and in water/N,N-dimethylformamide solvents.展开更多
基金supported by the National Natural Science Foundation of China(no.91961110,22171122).
文摘We report the synthesis,crystal structure,optical properties,and photothermal conversion properties of an ultra-stable cuprous Cu_(12) cluster,namely{[Cu_(3)^(I)(HTC_(4)A)]_(2)[Cu_(6)^(I)(2-PyS)_(6)]}·H_(2)O(Cu_(12),H_(4)TC_(4)A=p-tertbutylthiacalix[4]arene,2-PySH=2-pyridinethiol),which was built from a pre-synthesized Cu_(6)^(I)(2-PyS)_(6)(Cu_(6))precursor and two Cu_(3)^(I)-HTC_(4)A polynuclear secondary building units(PSBUs).The Cu_(12) cluster features a sandwich-like framework in which the Cu_(6) core is double surface capped by forming six Cu-S bonds with two Cu_(3)^(I)-HTC_(4)A PSBUs.The“cluster-cluster”assembly strategy enables all the metal centers in the Cu_(12) cluster to be monovalent and efficient organic ligand protection makes the cuprous cluster stable in common solvents(alcohol,acetonitrile,acetone,CHCl_(3),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 Cu_(3)^(I)-HTC_(4)A PSBUs can tune the electron and hole distribution of the Cu_(6) core,which makes Cu_(12) a stable and efficient photothermal conversion material both in the solid state and in water/N,N-dimethylformamide solvents.
