Using 1,1?-bis(isoquinoline)-1,4-phenyldimethylenyl(BIQPM2+) cation as template, a new tetrameric(Bi4 I16)4-iodobismuthate-containing hybrid with formula of(BIQPM)2(Bi4 I16)·H2 O(1), has been prepared under solvo...Using 1,1?-bis(isoquinoline)-1,4-phenyldimethylenyl(BIQPM2+) cation as template, a new tetrameric(Bi4 I16)4-iodobismuthate-containing hybrid with formula of(BIQPM)2(Bi4 I16)·H2 O(1), has been prepared under solvothermal conditions. The centrosymmetric Bi4-4 I16 tetraanion is constructed from four edge-shared slightly distorted BiI6 octahedrons. Due to the presence of larger conjugated system(isoquinoline ring), strong π···π stacking interactions can be observed. Besides, strong I···I interactions can be monitored and extends the 0-D Bi4 I4-16 cluster to a quasi-1-D chain. The smaller energy gap of 2.13 eV is led by these non-covalent interactions. Its infrared emission might be caused by strong charge transfer between anions and cations. Furthermore, the reversible thermochromic behavior with low chromotropic temperature of 80 ℃ can be observed, whose mechanism was discussed.展开更多
The copper（Ⅱ） DPP adduct Cu（DPP）（DMF）2（H2O）-（ClO4）2 1 （DPP = 4,7-diphenyl-1, 10-phentheanthroline, DMF = N,N＇-dimethyl formamide） has been prepared by a direct synthetic method and structurally character...The copper（Ⅱ） DPP adduct Cu（DPP）（DMF）2（H2O）-（ClO4）2 1 （DPP = 4,7-diphenyl-1, 10-phentheanthroline, DMF = N,N＇-dimethyl formamide） has been prepared by a direct synthetic method and structurally characterized. It presents a mononuclear structure and crystallizes in triclinic, space group P1 with a = 9.8717（2）, b = 12.579, c = 14.7574（2） A, α = 67.976（6）,β = 82.031（9）, γ = 80.343（9）°, V = 1668.96（9）A, Z = 1, Dc= 1.495 g/cm^3,/t（MoKα） = 0.877 mm^-1, F（000） = 774, C60H64Cl4Cu2N8O221 Mr = 1502.09, the final R1= 0.0643 and wR2 = 0.1799 for 6153 observed reflections with 1 〉 2σ（1）. Structure analysis shows that copper atom presents an unusual fivecoordination of square pyramid geometry. The whole structure is stabilized by π-π stacking interactions and static attractive forces from [ClO4]-anions. Based on crystal data, quantum chemistry calculation on DFF/B3LPY level was used to reveal the electronic structure of 1.展开更多
A novel platinum（Ⅳ） complex [Ph3PEt]2[PtCl6] 1 obtained from the reaction of H2PtCl6 and [Ph3PEt]I （Ph3PEt^＋ = ethyl-triphenylphosphenonium） has been structurally characterized. It crystallizes in triclinic, spa...A novel platinum（Ⅳ） complex [Ph3PEt]2[PtCl6] 1 obtained from the reaction of H2PtCl6 and [Ph3PEt]I （Ph3PEt^＋ = ethyl-triphenylphosphenonium） has been structurally characterized. It crystallizes in triclinic, space group P1 with a = 10.20850（10）, b = 10.33870（10）, c = 10.814 .A a = 79.453（12）, β = 66.879（ 11 ）, γ = 72.461 （10）°, V = 998.14（9） A^3, Z = 1, Dc = 1.648 g/cm^3, μ（MoKa） = 4.025 mm^-1, F（000） = 490, C40H40Cl6P2Pt, Mr = 990.44, the final R = 0.0270 and wR = 0.0617 for 5787 observed reflections with 1 〉 2σ（Ⅰ）. Structure analysis indicates that the platinum atom almost has the ideal octahedral coordination geometry of PtCl6. The quaternary phosphate cations （Ph3PEt^＋） acting as counter ions are in combination with PtCl6 anions by static attracting forces and H-bonds. Upon the hydrogen bonds existing between cations and anions, the whole structure represents a chain-like construction. Based on the crystal data, quantum chemistry calculation at the DFT/B3LPY level was carded out to reveal the electronic structure of 1.展开更多
Two organically templated uranium phosphites, （C4H12N）（UO2）（HPO3）（NO3） （Mr = 486.16） 1 and （C16H36N）2（UO2）2（H2PO3）2（HPO3）（NO3）2 （Mr= 1390.95） 2, were prepared by evaporation from aqueous solution...Two organically templated uranium phosphites, （C4H12N）（UO2）（HPO3）（NO3） （Mr = 486.16） 1 and （C16H36N）2（UO2）2（H2PO3）2（HPO3）（NO3）2 （Mr= 1390.95） 2, were prepared by evaporation from aqueous solution of uranyl nitrate, phosphite acid and their respective organic ammonium hydroxids. Their structures were determined by single-crystal X-ray diffraction and further characterized by infrared and fluorescence spectroscopy. In 1, pentagonal [UO7] bipyramids share comers with three [HPO3]2- tetrahedra and one edge with a [NO3]- anion to form [（UO2）- （HPO3）（NO3）]^- ladder-like chains parallel to the b axis. The structure of 2 is also based upon one-dimensional anionic [（UO2）2（H2PO3）2（HPO3）（NO3）2]2-chains of comer-sharing penta- gonal [UOT] bipyramids with [H2PO3]- and [HPO3] tetrahedra, which is still unknown in structural chemistry of uranium so far. Crystal data for 1： monoclinic, space group C2/m, a = 21.808（7）, b = 6.9605（15）, c = 8.357（2） A, β = 98.327（15）°, V= 1255.2（6） A^3, Z = 4, Dc = 2.573 g/cm^3, F（000） = 888, μ = 13.086 mm^-1 the final R = 0.0418 and wR = 0.0906 （I 〉 2σ（I））; and those for 2： monoclinic, space group C2/c, a = 36.4549（8）, b = 14.5296（11）, c = 20.8253（11） A, β = 101.7440（8）°, V= 10799.7（10） A3, Z = 8, Dc= 1.711 g/cm^3, F（000） = 5424,μ = 6.144 mm^-1, the final R= 0.0368 and wR= 0.0865 （I〉 2σ（I））.展开更多
Two triphenylmethylphosphonium/haloplumbate hybrids,i.e.,[(PPh3Me)2(Pb2I6)∙CH3CN]n(1)and[(PPh3Me)(PbBr3)]n(2),have been prepared,in which the(PbX3)nn-nanochains built from face-sharing PbX6 octahedra are surrounded by...Two triphenylmethylphosphonium/haloplumbate hybrids,i.e.,[(PPh3Me)2(Pb2I6)∙CH3CN]n(1)and[(PPh3Me)(PbBr3)]n(2),have been prepared,in which the(PbX3)nn-nanochains built from face-sharing PbX6 octahedra are surrounded by organic templates to assemble the core-shell quantum well.Besides,C−H…πinteractions among Ph3PMe+cations can also be detected,which give rise to the 2-D organic layer of 1 and 1-D chain for 2.The good water stabilities could be induced by the strong C−H…πinteractions,which can deter the hydrolysis reaction.The energy band gaps of this work mainly derive from the charge transfer of organic components,but their luminescence stems from the inorganic(PbX3)nn-nanochains with co-existence of free excitons and self-trapped excitons.At temperature lower than 117 K,strong quantum confinement will rule out the free excitons,and self-trapped excitons will dominate,resulting in red-shift luminescence.Moreover,effective and repeatable photocurrent responses can be found in these hybrids.展开更多
基金financially supported by the Teaching Quality Project of West Anhui Health Vocational College(YJZLGC201713)
文摘Using 1,1?-bis(isoquinoline)-1,4-phenyldimethylenyl(BIQPM2+) cation as template, a new tetrameric(Bi4 I16)4-iodobismuthate-containing hybrid with formula of(BIQPM)2(Bi4 I16)·H2 O(1), has been prepared under solvothermal conditions. The centrosymmetric Bi4-4 I16 tetraanion is constructed from four edge-shared slightly distorted BiI6 octahedrons. Due to the presence of larger conjugated system(isoquinoline ring), strong π···π stacking interactions can be observed. Besides, strong I···I interactions can be monitored and extends the 0-D Bi4 I4-16 cluster to a quasi-1-D chain. The smaller energy gap of 2.13 eV is led by these non-covalent interactions. Its infrared emission might be caused by strong charge transfer between anions and cations. Furthermore, the reversible thermochromic behavior with low chromotropic temperature of 80 ℃ can be observed, whose mechanism was discussed.
基金This work was supported by the Foundation of Education Committee of Fujian Province (NOS: JB03052, JB04016, JB04017) and the Student Research Training Program (SRTP)(NOS:03100)
文摘The copper（Ⅱ） DPP adduct Cu（DPP）（DMF）2（H2O）-（ClO4）2 1 （DPP = 4,7-diphenyl-1, 10-phentheanthroline, DMF = N,N＇-dimethyl formamide） has been prepared by a direct synthetic method and structurally characterized. It presents a mononuclear structure and crystallizes in triclinic, space group P1 with a = 9.8717（2）, b = 12.579, c = 14.7574（2） A, α = 67.976（6）,β = 82.031（9）, γ = 80.343（9）°, V = 1668.96（9）A, Z = 1, Dc= 1.495 g/cm^3,/t（MoKα） = 0.877 mm^-1, F（000） = 774, C60H64Cl4Cu2N8O221 Mr = 1502.09, the final R1= 0.0643 and wR2 = 0.1799 for 6153 observed reflections with 1 〉 2σ（1）. Structure analysis shows that copper atom presents an unusual fivecoordination of square pyramid geometry. The whole structure is stabilized by π-π stacking interactions and static attractive forces from [ClO4]-anions. Based on crystal data, quantum chemistry calculation on DFF/B3LPY level was used to reveal the electronic structure of 1.
基金This work was supported by the Foundation of Education Committee of Fujian Province (JB03052, JB04016, JB04017) and the Student Research Training Program (SRTP) (04075)
文摘A novel platinum（Ⅳ） complex [Ph3PEt]2[PtCl6] 1 obtained from the reaction of H2PtCl6 and [Ph3PEt]I （Ph3PEt^＋ = ethyl-triphenylphosphenonium） has been structurally characterized. It crystallizes in triclinic, space group P1 with a = 10.20850（10）, b = 10.33870（10）, c = 10.814 .A a = 79.453（12）, β = 66.879（ 11 ）, γ = 72.461 （10）°, V = 998.14（9） A^3, Z = 1, Dc = 1.648 g/cm^3, μ（MoKa） = 4.025 mm^-1, F（000） = 490, C40H40Cl6P2Pt, Mr = 990.44, the final R = 0.0270 and wR = 0.0617 for 5787 observed reflections with 1 〉 2σ（Ⅰ）. Structure analysis indicates that the platinum atom almost has the ideal octahedral coordination geometry of PtCl6. The quaternary phosphate cations （Ph3PEt^＋） acting as counter ions are in combination with PtCl6 anions by static attracting forces and H-bonds. Upon the hydrogen bonds existing between cations and anions, the whole structure represents a chain-like construction. Based on the crystal data, quantum chemistry calculation at the DFT/B3LPY level was carded out to reveal the electronic structure of 1.
基金the National Natural Science Foundation of China(51703120)Natural Science Foundation of Fujian Province(2021J011117)+1 种基金Education and Research Project of Fujian Province(JAT200640,B202031)Innovation and Entrepreneurship Training Program for College Students(202111311017)。
文摘Two organically templated uranium phosphites, （C4H12N）（UO2）（HPO3）（NO3） （Mr = 486.16） 1 and （C16H36N）2（UO2）2（H2PO3）2（HPO3）（NO3）2 （Mr= 1390.95） 2, were prepared by evaporation from aqueous solution of uranyl nitrate, phosphite acid and their respective organic ammonium hydroxids. Their structures were determined by single-crystal X-ray diffraction and further characterized by infrared and fluorescence spectroscopy. In 1, pentagonal [UO7] bipyramids share comers with three [HPO3]2- tetrahedra and one edge with a [NO3]- anion to form [（UO2）- （HPO3）（NO3）]^- ladder-like chains parallel to the b axis. The structure of 2 is also based upon one-dimensional anionic [（UO2）2（H2PO3）2（HPO3）（NO3）2]2-chains of comer-sharing penta- gonal [UOT] bipyramids with [H2PO3]- and [HPO3] tetrahedra, which is still unknown in structural chemistry of uranium so far. Crystal data for 1： monoclinic, space group C2/m, a = 21.808（7）, b = 6.9605（15）, c = 8.357（2） A, β = 98.327（15）°, V= 1255.2（6） A^3, Z = 4, Dc = 2.573 g/cm^3, F（000） = 888, μ = 13.086 mm^-1 the final R = 0.0418 and wR = 0.0906 （I 〉 2σ（I））; and those for 2： monoclinic, space group C2/c, a = 36.4549（8）, b = 14.5296（11）, c = 20.8253（11） A, β = 101.7440（8）°, V= 10799.7（10） A3, Z = 8, Dc= 1.711 g/cm^3, F（000） = 5424,μ = 6.144 mm^-1, the final R= 0.0368 and wR= 0.0865 （I〉 2σ（I））.
基金the National Natural Science Foundation of China(No.22078065)。
文摘Two triphenylmethylphosphonium/haloplumbate hybrids,i.e.,[(PPh3Me)2(Pb2I6)∙CH3CN]n(1)and[(PPh3Me)(PbBr3)]n(2),have been prepared,in which the(PbX3)nn-nanochains built from face-sharing PbX6 octahedra are surrounded by organic templates to assemble the core-shell quantum well.Besides,C−H…πinteractions among Ph3PMe+cations can also be detected,which give rise to the 2-D organic layer of 1 and 1-D chain for 2.The good water stabilities could be induced by the strong C−H…πinteractions,which can deter the hydrolysis reaction.The energy band gaps of this work mainly derive from the charge transfer of organic components,but their luminescence stems from the inorganic(PbX3)nn-nanochains with co-existence of free excitons and self-trapped excitons.At temperature lower than 117 K,strong quantum confinement will rule out the free excitons,and self-trapped excitons will dominate,resulting in red-shift luminescence.Moreover,effective and repeatable photocurrent responses can be found in these hybrids.
