Two 2D coordination sheets with pure Cu^(I)and mixed Cu^(I)/Cu^(II)centres based on tetranuclear cuprofullerene pentafluorobenzoate were realized under solvothermal conditions.They were constructed with linear(μ^(2)-...Two 2D coordination sheets with pure Cu^(I)and mixed Cu^(I)/Cu^(II)centres based on tetranuclear cuprofullerene pentafluorobenzoate were realized under solvothermal conditions.They were constructed with linear(μ^(2)-η^(2):η^(2))_(2)-C_(6)0 connecting Cu^(I)/Cu^(II)pentafluorobenzoate infinite chains.They exhibited optical absorptions covering the whole visible light and even the near-infrared region.Density functional theory(DFT)calculations revealed indirect characteristic with narrow bandgaps of 0.95 eV and 0.86 eV.The 3d-orbitals of Cu^(I)atoms and 2p-orbitals of C atoms from C_(6)0 molecules contributed dominantly to the valence band maximum(VBM)and conduction band minimum(CBM),consistent with the calculated frontier orbitals with the tetranuclear cuperfullerene pentafluorobenzoate model and optical absorptions.This work provides the structural diversity of cuprofullerenes and an effective strategy for constructing polymeric materials based on exohedral metallofullerenes(ExMFs).展开更多
基金supported by the National Natural Science Foundation of China(No.21731002,21975104,22150004,22071141)the Guangdong Major Project of Basic and Applied Research(No.2019B030302009)+1 种基金the Guangdong Basic and Applied Basic Research Foundation(No.2019A1515012162)the Open Fund of Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications(No.2020A05).
文摘Two 2D coordination sheets with pure Cu^(I)and mixed Cu^(I)/Cu^(II)centres based on tetranuclear cuprofullerene pentafluorobenzoate were realized under solvothermal conditions.They were constructed with linear(μ^(2)-η^(2):η^(2))_(2)-C_(6)0 connecting Cu^(I)/Cu^(II)pentafluorobenzoate infinite chains.They exhibited optical absorptions covering the whole visible light and even the near-infrared region.Density functional theory(DFT)calculations revealed indirect characteristic with narrow bandgaps of 0.95 eV and 0.86 eV.The 3d-orbitals of Cu^(I)atoms and 2p-orbitals of C atoms from C_(6)0 molecules contributed dominantly to the valence band maximum(VBM)and conduction band minimum(CBM),consistent with the calculated frontier orbitals with the tetranuclear cuperfullerene pentafluorobenzoate model and optical absorptions.This work provides the structural diversity of cuprofullerenes and an effective strategy for constructing polymeric materials based on exohedral metallofullerenes(ExMFs).
