The title compound C_6H(15)N_4O_2·BF_4, Mr=262.03,crystallized in orthorhombic belonging to space group P2_12_12_1,a=5.050(2),b=13.619(6),c=16.470(3)A.V=1133(1)A;Z=4 ;Dc=1. 536 gcm-3,F(000)=544,μ=1.462 cm￣(-1)(...The title compound C_6H(15)N_4O_2·BF_4, Mr=262.03,crystallized in orthorhombic belonging to space group P2_12_12_1,a=5.050(2),b=13.619(6),c=16.470(3)A.V=1133(1)A;Z=4 ;Dc=1. 536 gcm-3,F(000)=544,μ=1.462 cm￣(-1)(MoKα).The final R=0.082 and Rw=0. 081 for 673 independent observed reflections with I≥3σ(Ⅰ).The title compound is a 1:1 ionic complex of L-arginine and fluoroborate,and both the amino and guanidyl groups of L-arginine are protonated. There are a lot of hydrogen bonds in this crystal which link the discrete L-arginine and fluoroborate to form a three-dimensional network.展开更多
A coupled 1,4-dihydrylpyridine compound（C40H48N2O10,1） has been synthesized.Its structure was determined by single-crystal X-ray diffraction.The crystal is of monoclinic system,space group P21/c with a = 8.3300（2）...A coupled 1,4-dihydrylpyridine compound（C40H48N2O10,1） has been synthesized.Its structure was determined by single-crystal X-ray diffraction.The crystal is of monoclinic system,space group P21/c with a = 8.3300（2）,b = 15.720（3）,c = 14.480（3）,β = 90.08（3）°,V = 1896.1（7） 3,Z = 2,Mr = 716.80,Dc = 1.255 g/cm3,and F（000） = 764.The structure was solved by direct methods and refined by full-matrix least-squares method to the final R = 0.0556 and wR = 0.1499（I 2σ（I））.There exist several supramolecular motifs in the crystal structure.The compound exhibits strong photoluminescence in the solid state at room temperature.展开更多
Three new transition metal tricyanomethanide complexes [Co（dpdo）（tcm）2] （1）, [Cu（dpdo）（tcm）2] （2） and Cu（dpdo）2（tcm）2 （3） were synthesized and structurally characterized. In compound 1 each Co（II） ...Three new transition metal tricyanomethanide complexes [Co（dpdo）（tcm）2] （1）, [Cu（dpdo）（tcm）2] （2） and Cu（dpdo）2（tcm）2 （3） were synthesized and structurally characterized. In compound 1 each Co（II） ion is coordinated to four disorder tcm anions and one dpdo molecule to give a distorted octahedral geometry. In compound 2 each Cu（II） ion is surrounded by four tcm anions and one dpdo ligand to form a square bipyramidal geometry. Both compounds 1 and 2 display a μ1,5-tcm bridged infinite chain structure. Interestingly, in compound 3 coordination geometry around the central ion is square-planar, each Cu（II） ion is coordinated by two dpdo molecules to form a cationic part, the cationic parts is linked with the free tcm anionic parts via electrostatic attraction, leading to the formation of a mononuclear structure. Magnetic susceptibility measurement in the range 2--300 K indicates that there are antiferromagnetic couplings between adjacent metal ions in 1 （0=--2.33 K, C=2.13 cm3-mol 1oK） and 2 （J= --0.30, g = 2.20） respectively.展开更多
Two metal-organic frameworks [（Zn0.5L）·（H2O）]n （1） and [（Ni0.5L）？（H2O）]n （2） constructed by the 3-formyl-4-（pyridin-4-yl） benzoic acid ligand （HL） were synthesized and characterized by single-cry...Two metal-organic frameworks [（Zn0.5L）·（H2O）]n （1） and [（Ni0.5L）？（H2O）]n （2） constructed by the 3-formyl-4-（pyridin-4-yl） benzoic acid ligand （HL） were synthesized and characterized by single-crystal X-ray diffraction. 1 crystallizes in orthorhombic space group Pnna with a = 16.6152（8）, b = 12.6825（6）, c = 15.3908（8） A, V = 3243.2（3） ？3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F（000） = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ（I）. 2 is isostructural to 1, which also crystallizes in orthorhombic space group Pnna with a = 16.6152（8）, b = 12.6825（6）, c = 15.3908（8） ？, V = 3243.2（3） ？3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F（000） = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ（I）. Additionally, thermogravimetric analysis, FT-IR spectroscopy and powder X-ray diffraction were discussed.展开更多
Two 1D and one 3D coordination polymers,namely[Ni2(μ3-deta)(H2 biim)3(H2O)2]n(1),{[Zn2(μ4-deta)(Phen)2(H2O)]·H2O}n(2)and[Cd2(μ6-deta)(Phen)2(H2O)]n(3),have been constructed hydrothermally using H4deta(H4deta=2...Two 1D and one 3D coordination polymers,namely[Ni2(μ3-deta)(H2 biim)3(H2O)2]n(1),{[Zn2(μ4-deta)(Phen)2(H2O)]·H2O}n(2)and[Cd2(μ6-deta)(Phen)2(H2O)]n(3),have been constructed hydrothermally using H4deta(H4deta=2,3,3’,4’-diphenyl ether tetracarboxylic acid),H2 biim(H2 biim=2,2’-biimidazole),phen(phen=1,10-phenanthroline),and nickel,zinc or cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and characterized by IR spectra,elemental analyses,thermogravimetric analyses(TGA)and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group■.Compounds 1 and 2 disclose a 1D chain structure.Compound 3 features a 3D framework.The structural diversity of compounds 1~3 is driven by the metal(Ⅱ)node and the type of supporting ligand.Magnetic studies for compound 1 demonstrate an antiferromagnetic coupling between the adjacent Ni(Ⅱ)centers.The luminescence behavior of compounds 2 and 3 was also investigated.展开更多
A porous polymeric ligand(PPL)has been synthesized and complexed with copper to generate a heterogeneous catalyst(Cu@PPL)that has facilitated the efficient C-N coupling with various(hetero)aryl chlorides under mild co...A porous polymeric ligand(PPL)has been synthesized and complexed with copper to generate a heterogeneous catalyst(Cu@PPL)that has facilitated the efficient C-N coupling with various(hetero)aryl chlorides under mild conditions of visiblelight irradiation at 80°C(58 examples,up to 99%yields).This method could be applied to both aqueous ammonia and substituted amines,and is compatible to a variety of functional groups and heterocycles,as well as allows tandem C-N couplings with conjunctive dihalides.Furthermore,the heterogeneous characteristic of Cu@PPL has enabled a straightforward catalyst separation in multiple times of recycling with negligible catalytic efficiency loss by simple filtration,affording reaction mixtures containing less than 1 ppm of Cu residue.展开更多
The third-order nonlinear optical(NLO)materials with stimuli-responsive properties have received extraordinary attention due to their controllable photophysical properties.In this work,two attractive metal complexes t...The third-order nonlinear optical(NLO)materials with stimuli-responsive properties have received extraordinary attention due to their controllable photophysical properties.In this work,two attractive metal complexes third-order NLO switches,which are far superior to congeneric optical switches in terms of their performance conversion,versatility,and fast response,were successfully designed and synthesized.The test of their third-order NLO properties proves that the metal complexes exhibit reverse saturable absorption and self-defocusing refraction.After light irradiation,the third-order NLO behavior turns quickly into self-focusing refraction.The relation between the molecular structures and the third-order NLO properties was investigated via1H nuclear magnetic resonance and ultraviolet-visible absorption.The results show that the metal ions have a significant influence on the NLO behavior and reveal the origin of third-order NLO properties via Z-scan determinations,pump-probe technology,and density functional theory calculations.These metal complexes can be used as third-order NLO switches with excellent fatigue resistance and broaden the application range of third-order NLO materials with adjustable performances.展开更多
The flexibility of metal-organic frameworks(MOFs)featuring stimuli-responsive structural transitions is often governed not only by the chemical composition and topology but also by orthogonal factors such as particle ...The flexibility of metal-organic frameworks(MOFs)featuring stimuli-responsive structural transitions is often governed not only by the chemical composition and topology but also by orthogonal factors such as particle size,desolvation method,and history of the sample.A precise understanding of the mechanism behind such observations has been lacking up to now,and there are still substantial open questions concerning the impact of sample treatment history.The DUT-8(M)family([M_(2)(2,6-ndc)2(dabco)]n,2,6-ndc=2,6-naphthalene dicarboxylate,dabco=1,4-diazabicyclo-[2.2.2]-octane),encompasses isostructural compounds based on Ni,Zn,Co,and Cu in the cluster node and is representative of pillared layer MOFs,often showing flexible behavior.In this contribution,we discuss a possible explanation for the differences in flexibility observed in desolvated phases of DUT-8(Cu).Theoretical calculations and crystallographic data shed light on the preferred formation of interpenetrated confined closed pore phases in DUT-8(Cu)in contrast to DUT-8(Ni,Co,Zn)where the closed pore phases are formed.展开更多
The addition-hydrolysis reaction of benzimidazolium salt with some mono- and bifunctional amine nucleophiles is reported, and a novel method of biomimetic synthesis for formamides and heterocycle compounds is provided.
The preparation of hybrid mesoporous MCM-48 grafted by vinyl group via post-grafting process was reported and studied by X-ray diffraction, BET and 29Si solid MAS NMR.An organic β-diketonate Europium complex the corr...The preparation of hybrid mesoporous MCM-48 grafted by vinyl group via post-grafting process was reported and studied by X-ray diffraction, BET and 29Si solid MAS NMR.An organic β-diketonate Europium complex the corresponding luminescence property was characterized.展开更多
(H2NC2H4NH2)2Ni [(C3H3N2) Co (NH3)5]2 (CIO4)6 · 5H2O,NiCo2Cl6O29N18C10H62, Mr = 1288. 00, monoclinic, C2/c, a = 31. 832(4), b = 9. 691 (1), c=15. 425(4)(?),β=90. 71(2)°, Z = 4, V = 4758. 0(?)3, Dc=1. 798g/c...(H2NC2H4NH2)2Ni [(C3H3N2) Co (NH3)5]2 (CIO4)6 · 5H2O,NiCo2Cl6O29N18C10H62, Mr = 1288. 00, monoclinic, C2/c, a = 31. 832(4), b = 9. 691 (1), c=15. 425(4)(?),β=90. 71(2)°, Z = 4, V = 4758. 0(?)3, Dc=1. 798g/cm3, μ (MoKa) = 15. 22cm-1, F(000)=2656. The three metal nuclei, one Ni( Ⅱ ) and two Co( Ⅲ ), bridged by two imidazolyl anions (Im = C3H3N2), form an isosceles triangle. The Ni( Ⅱ ) atom is situated on the two-fold axis and coordinated by six nitrogen atoms to form a distorted octahedron with two nitrogen atoms from two Im in cis-positions. The two Co( Ⅲ ) atoms are related by C2 symmetry and each Co( Ⅲ ) is coordinated by six nitrogen atoms to form an octahedral configuration.展开更多
文摘The title compound C_6H(15)N_4O_2·BF_4, Mr=262.03,crystallized in orthorhombic belonging to space group P2_12_12_1,a=5.050(2),b=13.619(6),c=16.470(3)A.V=1133(1)A;Z=4 ;Dc=1. 536 gcm-3,F(000)=544,μ=1.462 cm￣(-1)(MoKα).The final R=0.082 and Rw=0. 081 for 673 independent observed reflections with I≥3σ(Ⅰ).The title compound is a 1:1 ionic complex of L-arginine and fluoroborate,and both the amino and guanidyl groups of L-arginine are protonated. There are a lot of hydrogen bonds in this crystal which link the discrete L-arginine and fluoroborate to form a three-dimensional network.
基金supported by the Key Project of Chinese Ministry of Education (No.208116)the Scientific and Technological Project of CQEC (No.KJ080829)the Chongqing Normal University Scientific Research Foundation Project (No.06XLY016)
文摘A coupled 1,4-dihydrylpyridine compound（C40H48N2O10,1） has been synthesized.Its structure was determined by single-crystal X-ray diffraction.The crystal is of monoclinic system,space group P21/c with a = 8.3300（2）,b = 15.720（3）,c = 14.480（3）,β = 90.08（3）°,V = 1896.1（7） 3,Z = 2,Mr = 716.80,Dc = 1.255 g/cm3,and F（000） = 764.The structure was solved by direct methods and refined by full-matrix least-squares method to the final R = 0.0556 and wR = 0.1499（I 2σ（I））.There exist several supramolecular motifs in the crystal structure.The compound exhibits strong photoluminescence in the solid state at room temperature.
基金Project supported by the National Natural Science Foundation of China （No. 20571086）.
文摘Three new transition metal tricyanomethanide complexes [Co（dpdo）（tcm）2] （1）, [Cu（dpdo）（tcm）2] （2） and Cu（dpdo）2（tcm）2 （3） were synthesized and structurally characterized. In compound 1 each Co（II） ion is coordinated to four disorder tcm anions and one dpdo molecule to give a distorted octahedral geometry. In compound 2 each Cu（II） ion is surrounded by four tcm anions and one dpdo ligand to form a square bipyramidal geometry. Both compounds 1 and 2 display a μ1,5-tcm bridged infinite chain structure. Interestingly, in compound 3 coordination geometry around the central ion is square-planar, each Cu（II） ion is coordinated by two dpdo molecules to form a cationic part, the cationic parts is linked with the free tcm anionic parts via electrostatic attraction, leading to the formation of a mononuclear structure. Magnetic susceptibility measurement in the range 2--300 K indicates that there are antiferromagnetic couplings between adjacent metal ions in 1 （0=--2.33 K, C=2.13 cm3-mol 1oK） and 2 （J= --0.30, g = 2.20） respectively.
基金supported by the National Natural Science Foundation of China(No.21371119,21431004,21401128,21522104,and 21620102001)the National Key Basic Research Program of China(No.2014CB932102 and 2016YFA0203400)the Shanghai“Eastern Scholar”Program
文摘Two metal-organic frameworks [（Zn0.5L）·（H2O）]n （1） and [（Ni0.5L）？（H2O）]n （2） constructed by the 3-formyl-4-（pyridin-4-yl） benzoic acid ligand （HL） were synthesized and characterized by single-crystal X-ray diffraction. 1 crystallizes in orthorhombic space group Pnna with a = 16.6152（8）, b = 12.6825（6）, c = 15.3908（8） A, V = 3243.2（3） ？3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F（000） = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ（I）. 2 is isostructural to 1, which also crystallizes in orthorhombic space group Pnna with a = 16.6152（8）, b = 12.6825（6）, c = 15.3908（8） ？, V = 3243.2（3） ？3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F（000） = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ（I）. Additionally, thermogravimetric analysis, FT-IR spectroscopy and powder X-ray diffraction were discussed.
基金supported by Guangdong Province Higher Vocational Colleges&Schools Pearl River Scholar Funded Scheme(2015,2018)the Pearl River Scholar Foundation of Guangdong Industry Polytechnic(RC2015-001)+4 种基金the Opening Foundation of MOE Key Laboratory of Bioinorganic and Synthetic Chemistry(2016)Innovation Team Project on University of Guangdong Province(2017GKCXTD001)Science and Technology Planning Project of Guangzhou(201904010381)the Science and Technology Innovation Project of Guangdong University Student(pdjh2019b0690)Shenzhen Science and Technology Plan Project(JCYJ20170817112445033,GGFW2017041209483817)。
文摘Two 1D and one 3D coordination polymers,namely[Ni2(μ3-deta)(H2 biim)3(H2O)2]n(1),{[Zn2(μ4-deta)(Phen)2(H2O)]·H2O}n(2)and[Cd2(μ6-deta)(Phen)2(H2O)]n(3),have been constructed hydrothermally using H4deta(H4deta=2,3,3’,4’-diphenyl ether tetracarboxylic acid),H2 biim(H2 biim=2,2’-biimidazole),phen(phen=1,10-phenanthroline),and nickel,zinc or cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and characterized by IR spectra,elemental analyses,thermogravimetric analyses(TGA)and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group■.Compounds 1 and 2 disclose a 1D chain structure.Compound 3 features a 3D framework.The structural diversity of compounds 1~3 is driven by the metal(Ⅱ)node and the type of supporting ligand.Magnetic studies for compound 1 demonstrate an antiferromagnetic coupling between the adjacent Ni(Ⅱ)centers.The luminescence behavior of compounds 2 and 3 was also investigated.
基金the National Natural Science Foundation of China(21704016,21971044)。
文摘A porous polymeric ligand(PPL)has been synthesized and complexed with copper to generate a heterogeneous catalyst(Cu@PPL)that has facilitated the efficient C-N coupling with various(hetero)aryl chlorides under mild conditions of visiblelight irradiation at 80°C(58 examples,up to 99%yields).This method could be applied to both aqueous ammonia and substituted amines,and is compatible to a variety of functional groups and heterocycles,as well as allows tandem C-N couplings with conjunctive dihalides.Furthermore,the heterogeneous characteristic of Cu@PPL has enabled a straightforward catalyst separation in multiple times of recycling with negligible catalytic efficiency loss by simple filtration,affording reaction mixtures containing less than 1 ppm of Cu residue.
基金the National Natural Science Foundation of China(21671174 and U1904172)the Zhongyuan Thousand Talents Project,the Natural Science Foundation of Henan Province(182300410008)the Open Foundation of Guangxi Key Laboratory of Processing for Nonferrous Metals and Featured Materials,Guangxi University(2019GXYSOF12).
文摘The third-order nonlinear optical(NLO)materials with stimuli-responsive properties have received extraordinary attention due to their controllable photophysical properties.In this work,two attractive metal complexes third-order NLO switches,which are far superior to congeneric optical switches in terms of their performance conversion,versatility,and fast response,were successfully designed and synthesized.The test of their third-order NLO properties proves that the metal complexes exhibit reverse saturable absorption and self-defocusing refraction.After light irradiation,the third-order NLO behavior turns quickly into self-focusing refraction.The relation between the molecular structures and the third-order NLO properties was investigated via1H nuclear magnetic resonance and ultraviolet-visible absorption.The results show that the metal ions have a significant influence on the NLO behavior and reveal the origin of third-order NLO properties via Z-scan determinations,pump-probe technology,and density functional theory calculations.These metal complexes can be used as third-order NLO switches with excellent fatigue resistance and broaden the application range of third-order NLO materials with adjustable performances.
基金made possible as a result of a generous grant from the German Research Foundation(grant no.279409724).
文摘The flexibility of metal-organic frameworks(MOFs)featuring stimuli-responsive structural transitions is often governed not only by the chemical composition and topology but also by orthogonal factors such as particle size,desolvation method,and history of the sample.A precise understanding of the mechanism behind such observations has been lacking up to now,and there are still substantial open questions concerning the impact of sample treatment history.The DUT-8(M)family([M_(2)(2,6-ndc)2(dabco)]n,2,6-ndc=2,6-naphthalene dicarboxylate,dabco=1,4-diazabicyclo-[2.2.2]-octane),encompasses isostructural compounds based on Ni,Zn,Co,and Cu in the cluster node and is representative of pillared layer MOFs,often showing flexible behavior.In this contribution,we discuss a possible explanation for the differences in flexibility observed in desolvated phases of DUT-8(Cu).Theoretical calculations and crystallographic data shed light on the preferred formation of interpenetrated confined closed pore phases in DUT-8(Cu)in contrast to DUT-8(Ni,Co,Zn)where the closed pore phases are formed.
基金This work was supported by the National Natural Science Foundation of China(NO.20172041)Provincial Natural Science Foundation of Shaanxi Province.
文摘The addition-hydrolysis reaction of benzimidazolium salt with some mono- and bifunctional amine nucleophiles is reported, and a novel method of biomimetic synthesis for formamides and heterocycle compounds is provided.
基金Project supported by the National Natural Science Foundation of China (20171043,20372060), Key National Natural Science Foundation of China ( 20131010 ) and" 863" National Foundation for High Technology Development and Programming(2002AA302105, 2002AA3240
文摘The preparation of hybrid mesoporous MCM-48 grafted by vinyl group via post-grafting process was reported and studied by X-ray diffraction, BET and 29Si solid MAS NMR.An organic β-diketonate Europium complex the corresponding luminescence property was characterized.
文摘(H2NC2H4NH2)2Ni [(C3H3N2) Co (NH3)5]2 (CIO4)6 · 5H2O,NiCo2Cl6O29N18C10H62, Mr = 1288. 00, monoclinic, C2/c, a = 31. 832(4), b = 9. 691 (1), c=15. 425(4)(?),β=90. 71(2)°, Z = 4, V = 4758. 0(?)3, Dc=1. 798g/cm3, μ (MoKa) = 15. 22cm-1, F(000)=2656. The three metal nuclei, one Ni( Ⅱ ) and two Co( Ⅲ ), bridged by two imidazolyl anions (Im = C3H3N2), form an isosceles triangle. The Ni( Ⅱ ) atom is situated on the two-fold axis and coordinated by six nitrogen atoms to form a distorted octahedron with two nitrogen atoms from two Im in cis-positions. The two Co( Ⅲ ) atoms are related by C2 symmetry and each Co( Ⅲ ) is coordinated by six nitrogen atoms to form an octahedral configuration.
