The novel alkaline metal complex Ca（BPDCH）2 （1, BPDCH2 = 2,2＇-bipyri- dine-5,5＇-dicarboxylic acid） has been synthesized by the hydrothermal reaction of Ca（NO3）2·4H2O with 2,2＇-bipyridine-5,5＇-dicarboxyl...The novel alkaline metal complex Ca（BPDCH）2 （1, BPDCH2 = 2,2＇-bipyri- dine-5,5＇-dicarboxylic acid） has been synthesized by the hydrothermal reaction of Ca（NO3）2·4H2O with 2,2＇-bipyridine-5,5＇-dicarboxylic acid. The molecular and crystal structures of complex 1 have firstly been characterized by FTIR, elemental analysis, and X-ray single-crystal diffraction. The 3D MOF structure of complex 1 was interpreted by the versatile binding modes-the intermolecular hydrogen bonds and π-π stacking interactions of 2,2＇-bipyridine-5,5＇-dicarboxylic acid ligand. The analysis results show complex 1 belongs to a coordination polymer with 3D MOF structure. The results of thermogravimetric analysis and solubility demonstrate complex 1 is a thermostable compound and does not dissolve in water and traditional organic solvents.展开更多
Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-...Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-1,2-bis（4-pyridyl）ethene） and [（PPh3）2Cu2（μ-Cl）2（μ-bpe）]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1^- with a = 9.122（3）, b = 9.322（3）, c = 13.201（4） A, α = 106.440（4）, β= 105.965（5）, γ= 94.167（5）°, V = 1021.3（6） A^3, Mr= 967.62, Z = 1, De= 1.573 g/cm^3, F（000） = 486, μ = 3.111 mm^-1, the final R = 0.0383 and ωR = 0.0960 for 2792 observed reflections （I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1^- with a = 9.420（3）, b = 10.209（4）, c = 12.407（4） A, α = 104.136（6）, β = 108.132（5）, γ= 95.338（6）°, V = 1081.0（7） A^3, Mr= 496.83, Z = 2, Dc= 1.526 g/cm^3, F（000） = 500, μ = 2.941 mm^-1, the final R = 0.0445 and ωR = 0.1117 for 3251 observed reflections （I 〉 2σ（I））. Complex 3 crystallizes in triclinic, space group P1^- with a = 8.32（1）, b = 11.53（2）, c = 13.94（3） A, α = 109.57（3）, β= 93.85（3）, γ= 97.28（3）°, V= 1242（4） A^3, Mr= 1074.59, Z = 1, Dc = 1.436 g/cm^3, F（000） = 548, μ = 1.279 mm^-1, the final R = 0.0786 and ωR = 0.1586 for 2266 observed reflections （I 〉 2σ（I））. The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand （IL） and metal-to-ligand charge-transfer （MLCT） excited state.展开更多
Reaction of bis（4,6-dimethyl-2-pyrimidinethiolato）methane（bpytm） with CuCl2·4H2O in a mixed methanol/dichloromethane solution gave a one-dimensional coordina-tion polymer [CuCl2（μ-bpytm）]n which was charac...Reaction of bis（4,6-dimethyl-2-pyrimidinethiolato）methane（bpytm） with CuCl2·4H2O in a mixed methanol/dichloromethane solution gave a one-dimensional coordina-tion polymer [CuCl2（μ-bpytm）]n which was characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/c with a=16.9433（5）,b=13.6986（4）,c=7.8434（2）,β=100.371（2）°,V=1790.71（9）3,Z=4,Mr=426.86,Dc=1.583 g/cm3,μ（MoKα）=1.751mm-1,F（000）=868,S=1.025,the final R=0.0399 and wR=0.0924 for 2538 observed reflections with Ⅰ〉2σ（I） and 206 variables. The neutral coordination polymer is constructed by the bidentate thioether ligands to link adjacent copper atoms. Each copper atom is bridged by two adjacent nitrogen atoms of bpytm ligands and terminally bonded by two chloride atoms to form a squareplanar coordination geometry. The average Cu-N and Cu-CI bond lengths are 2.025（2） and 2.234（1） A, respectively.展开更多
Three polymer-amphiphile complexes were prepared by combining poly（allylamine hydrochloride）（PAH） with the potassium salt of mono-,di-,and trisubstituted benzoic acid dendrons（4-octyloxybenzoic acid,3,5-dioctylox...Three polymer-amphiphile complexes were prepared by combining poly（allylamine hydrochloride）（PAH） with the potassium salt of mono-,di-,and trisubstituted benzoic acid dendrons（4-octyloxybenzoic acid,3,5-dioctyloxybenzoic acid,and 3,4,5- trioctyloxybenzoic acid）.The solid structure and properties were monitored with FT-IR,XRD,TG,DSC,and polarized optical microscope（POM）.Difference in the tail chain number of the dendritic amphiphile induced two different mesomorphous structures： lamella for the mono-,disubstituted dendron containing complexes and hexagonal column for the trisubstituted dendron containing complexes.These corresponded to the ionic thermotropic liquid crystal SmA andΦ_h phases,respectively.This finding is significant for design of functional nanostructures based on the ionic complexation of polymers and amphiphiles.展开更多
The development and applications of materials with efficient circularly polarized luminescence(CPL)have become an interdisciplinary frontier research topic.We summarize herein the recent advance in the development and...The development and applications of materials with efficient circularly polarized luminescence(CPL)have become an interdisciplinary frontier research topic.We summarize herein the recent advance in the development and applications of CPLactive aggregates based on metal-ligand coordination materials(termed as“coordination aggregates”).The materials surveyed are classified as aggregates of smallmolecular metal complexes,which include monocomponent assemblies of Pt(II)complexes and other complexes and binary aggregates of metal complexes,and CPL-active metal-ligand coordination helicates,polymers,and frameworks.The efforts in improving the dissymmetry luminescence factors and quantum yields of these materials and the use of the aggregation strategy in enhancing the performance of isolated molecules are discussed.The recent applications of chiral metal complexes in circularly polarized organic light-emitting diodes(OLEDs)based on solution-or evaporation-processed procedures are surveyed.In addition,the uses of lanthanide complexes in CPL-contrast imaging and as CPL probes are highlighted.The common discussion on the mechanism of aggregation-enhanced CPLs and a perspective on future works of CPL-active coordination aggregates are finally given.展开更多
基金Supported by the National Natural Science Foundation of China(NSFC 21266019,NSFC 21062011)the Natural Science Fundation of Inner Mongolia(20080404MS020)Program for New Century Excellent Talents in University(NCET-08-858)
文摘The novel alkaline metal complex Ca（BPDCH）2 （1, BPDCH2 = 2,2＇-bipyri- dine-5,5＇-dicarboxylic acid） has been synthesized by the hydrothermal reaction of Ca（NO3）2·4H2O with 2,2＇-bipyridine-5,5＇-dicarboxylic acid. The molecular and crystal structures of complex 1 have firstly been characterized by FTIR, elemental analysis, and X-ray single-crystal diffraction. The 3D MOF structure of complex 1 was interpreted by the versatile binding modes-the intermolecular hydrogen bonds and π-π stacking interactions of 2,2＇-bipyridine-5,5＇-dicarboxylic acid ligand. The analysis results show complex 1 belongs to a coordination polymer with 3D MOF structure. The results of thermogravimetric analysis and solubility demonstrate complex 1 is a thermostable compound and does not dissolve in water and traditional organic solvents.
基金the State Key Project (No. 2005CCA06800)the NSFC/RGC Joint Research Foundation (50418010)
文摘Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-1,2-bis（4-pyridyl）ethene） and [（PPh3）2Cu2（μ-Cl）2（μ-bpe）]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1^- with a = 9.122（3）, b = 9.322（3）, c = 13.201（4） A, α = 106.440（4）, β= 105.965（5）, γ= 94.167（5）°, V = 1021.3（6） A^3, Mr= 967.62, Z = 1, De= 1.573 g/cm^3, F（000） = 486, μ = 3.111 mm^-1, the final R = 0.0383 and ωR = 0.0960 for 2792 observed reflections （I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1^- with a = 9.420（3）, b = 10.209（4）, c = 12.407（4） A, α = 104.136（6）, β = 108.132（5）, γ= 95.338（6）°, V = 1081.0（7） A^3, Mr= 496.83, Z = 2, Dc= 1.526 g/cm^3, F（000） = 500, μ = 2.941 mm^-1, the final R = 0.0445 and ωR = 0.1117 for 3251 observed reflections （I 〉 2σ（I））. Complex 3 crystallizes in triclinic, space group P1^- with a = 8.32（1）, b = 11.53（2）, c = 13.94（3） A, α = 109.57（3）, β= 93.85（3）, γ= 97.28（3）°, V= 1242（4） A^3, Mr= 1074.59, Z = 1, Dc = 1.436 g/cm^3, F（000） = 548, μ = 1.279 mm^-1, the final R = 0.0786 and ωR = 0.1586 for 2266 observed reflections （I 〉 2σ（I））. The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand （IL） and metal-to-ligand charge-transfer （MLCT） excited state.
基金supported by the Natural Science Foundation of the Education Bureau of Anhui Provincethe Program for New Century Excellent Talents in University (2006kj035a and NCET-06-0556)
文摘Reaction of bis（4,6-dimethyl-2-pyrimidinethiolato）methane（bpytm） with CuCl2·4H2O in a mixed methanol/dichloromethane solution gave a one-dimensional coordina-tion polymer [CuCl2（μ-bpytm）]n which was characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/c with a=16.9433（5）,b=13.6986（4）,c=7.8434（2）,β=100.371（2）°,V=1790.71（9）3,Z=4,Mr=426.86,Dc=1.583 g/cm3,μ（MoKα）=1.751mm-1,F（000）=868,S=1.025,the final R=0.0399 and wR=0.0924 for 2538 observed reflections with Ⅰ〉2σ（I） and 206 variables. The neutral coordination polymer is constructed by the bidentate thioether ligands to link adjacent copper atoms. Each copper atom is bridged by two adjacent nitrogen atoms of bpytm ligands and terminally bonded by two chloride atoms to form a squareplanar coordination geometry. The average Cu-N and Cu-CI bond lengths are 2.025（2） and 2.234（1） A, respectively.
基金the financial support from the NSFC(No50873037)the PCSIRT(NoIRT0827)+2 种基金the Fundamental Research Funds for the Central Universities(No2009ZM0017)China Postdoctoral Science Foundation(No20100470908)the NSF of Guangdong Province(No10451064101005118) is gratefully acknowledged
文摘Three polymer-amphiphile complexes were prepared by combining poly（allylamine hydrochloride）（PAH） with the potassium salt of mono-,di-,and trisubstituted benzoic acid dendrons（4-octyloxybenzoic acid,3,5-dioctyloxybenzoic acid,and 3,4,5- trioctyloxybenzoic acid）.The solid structure and properties were monitored with FT-IR,XRD,TG,DSC,and polarized optical microscope（POM）.Difference in the tail chain number of the dendritic amphiphile induced two different mesomorphous structures： lamella for the mono-,disubstituted dendron containing complexes and hexagonal column for the trisubstituted dendron containing complexes.These corresponded to the ionic thermotropic liquid crystal SmA andΦ_h phases,respectively.This finding is significant for design of functional nanostructures based on the ionic complexation of polymers and amphiphiles.
基金The Youth Project of Qujing Normal University(2013QN026)The Application Basis Research Key Project of Yunnan Province Science and Technology Department(201401CB00299)
基金National Natural Science Foundation of China,Grant/Award Numbers:21925112,22090021,21872154,21601194Beijing Natural Science Foundation,Grant/Award Number:2191003。
文摘The development and applications of materials with efficient circularly polarized luminescence(CPL)have become an interdisciplinary frontier research topic.We summarize herein the recent advance in the development and applications of CPLactive aggregates based on metal-ligand coordination materials(termed as“coordination aggregates”).The materials surveyed are classified as aggregates of smallmolecular metal complexes,which include monocomponent assemblies of Pt(II)complexes and other complexes and binary aggregates of metal complexes,and CPL-active metal-ligand coordination helicates,polymers,and frameworks.The efforts in improving the dissymmetry luminescence factors and quantum yields of these materials and the use of the aggregation strategy in enhancing the performance of isolated molecules are discussed.The recent applications of chiral metal complexes in circularly polarized organic light-emitting diodes(OLEDs)based on solution-or evaporation-processed procedures are surveyed.In addition,the uses of lanthanide complexes in CPL-contrast imaging and as CPL probes are highlighted.The common discussion on the mechanism of aggregation-enhanced CPLs and a perspective on future works of CPL-active coordination aggregates are finally given.
