A new gadolinium porous complex,(NH4)2[Gd2(pzdc)4(H2O)2],was synthesized through hydrothermal reaction of 2,3-pyrazinedicarboxylic acid and Gd(NO3)3·6 H2O with the pH value adjusted by ammonia.It was characterize...A new gadolinium porous complex,(NH4)2[Gd2(pzdc)4(H2O)2],was synthesized through hydrothermal reaction of 2,3-pyrazinedicarboxylic acid and Gd(NO3)3·6 H2O with the pH value adjusted by ammonia.It was characterized by elemental analysis,FT-IR,TGA and further by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group P21/c with a=14.249(7),b=15.889(8),c=12.846(7)A,β=95.724(10)°,V=2894(3)A^3,Z=4,Dc=2.385 g/cm^3,μ(Mo Ka)=4.65 mm^–1 and F(000)=1976.1976 reflections were measured and 6446 independent reflections(Rint=0.0985)were used in further refinement.The complex exhibits a 3D framework constructed from the[Gd2(pzdc)4(H2O)2]2-building blocks.It is scarce that the NH4+cations are located in the channels and balance the charge of anion framework.Furthermore,the ion exchange property of this complex has also been studied.The NH4+cations can be replaced by Na+cations,which is an uncommon phenomenon for gadolinium-containing porous complex.展开更多
One new mixed-ligand coordination polymer,namely[Co2（btc）（bpdc）（0.5）（py）3]n（1）,was hydrothermally synthesized using biphenyl-2,4,4＇-tricarboxylic acid（H3btc） as a main building block,along with two auxili...One new mixed-ligand coordination polymer,namely[Co2（btc）（bpdc）（0.5）（py）3]n（1）,was hydrothermally synthesized using biphenyl-2,4,4＇-tricarboxylic acid（H3btc） as a main building block,along with two auxiliary ligands（H2bpdc = 2,2＇-bipyridine-5,5＇-dicarboxylic acid and py =pyridine）.The product 1 was characterized by IR spectroscopy,elemental,thermogravimetric,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction studies show that compound 1 possesses an intricate 3D metal-organic framework based on tetracobalt（Ⅱ） units.Magnetic susceptibility measurement indicates that compound 1 shows an antiferromagnetic coupling between the Co（Ⅱ） ions.展开更多
Two novel lanthanide-organic polymers [Er2（pdc）2（o-bdc）（H2O）2]·H2O（1,H2pdc = 2,6-pyridinedicarboxylic acid,o-H2bdc = 1,2-benzenedicarboxylic acid） and Er（Himdc）（mbdc）0.5（H2O）（2,H3imdc = 4,5-imidazo...Two novel lanthanide-organic polymers [Er2（pdc）2（o-bdc）（H2O）2]·H2O（1,H2pdc = 2,6-pyridinedicarboxylic acid,o-H2bdc = 1,2-benzenedicarboxylic acid） and Er（Himdc）（mbdc）0.5（H2O）（2,H3imdc = 4,5-imidazoledicarboxylic acid,m-H2bdc = 1,3-benzenedicarboxylic acid） have been synthesized and characterized by elemental analysis,IR,thermogravimetric analysis and X-ray single-crystal diffraction studies.1 crystallizes in monoclinic,space group P21/c,while 2 in the orthorhombic space group Pbcn.Both compounds 1 and 2 display two-dimensional network structures. For 1, the tetranuclear parallelogram {Era} cluster as a building block is further assembled into a wonderful 2D grid, and the layers are interconnected via hydrogen bonds and π-π stacking interactions to yield a 3D supramolecular architecture; for 2, its configuration is a rare double-decker structure. These two complexes represent good examples for using mixcarboxylate-containing ligands to construct diverse 2D lanthanide coordination polymers.展开更多
The title Mn（Ⅱ） coordination polymer,poly{[heptaaqua-（μ4-bi-phenyl-3,3？,5,5？-tetracarboxylate）-bimanganese（Ⅱ）] pentahydrate},[Mn_2（bpta）（H_2O）_7]_n·5n H_2O（I）,is crystallized from a mixture of bi...The title Mn（Ⅱ） coordination polymer,poly{[heptaaqua-（μ4-bi-phenyl-3,3？,5,5？-tetracarboxylate）-bimanganese（Ⅱ）] pentahydrate},[Mn_2（bpta）（H_2O）_7]_n·5n H_2O（I）,is crystallized from a mixture of biphenyl-3,3？,5,5？-tetracarboxylic acid（H_4bpta） and MnCl_2·4H_2O in waterethanol under room temperature. Its asymmetric unit consists of one and two halves of crystallographically independent Mn（Ⅱ） cations,one fully deprotonated H4 bpta ligand,seven coordinated water molecules and five solvent water as guest molecules. In I,each Mn（Ⅱ） atom is octahedrally coordinated by six oxygen atoms from bpta^（4-） anions and coordinated water molecules. In the Mn（Ⅱ） cations,one half Mn（Ⅱ） ion of them located at a 2-fold axis generating a trinuclear [Mn_3（H_2O）_2（RCOO）_2] linker by μ1,1-O（water） and μ1,3-O,O？（carboxylate） bridges and another half Mn（Ⅱ） ion with an inversion is a mononuclear linker. These neighbouring trinuclear and mononuclear Mn（Ⅱ） cations are linked together by biphenyl-3,3？,5,5？-tetracarboxylates to form a three-dimensional framework with a（42.84） topology of a（4,4）-connected net,in which the positions of the trinuclear [Mn_3（H_2O）_2（R-COO）_2] linker as a 4-connector linking four bpta^（4-） ligands in I reproduce an eagle-shaped arrangement. The polymeric structure exhibits a water channel with an accessible void of 797.1 ？~3,amounting to 15.7% of the total unit-cell volume. Each of the cavities in the network is occupied by solvent water molecules.展开更多
A new aromatic carboxylate ligand,namely 5-（pyrrolidin-1-yl）-1,3-benzenedicar-boxylic acid（H2pybdc）,was synthesized and characterized by FT-IR and single-crystal X-ray diffraction analysis.It crystallizes in tricl...A new aromatic carboxylate ligand,namely 5-（pyrrolidin-1-yl）-1,3-benzenedicar-boxylic acid（H2pybdc）,was synthesized and characterized by FT-IR and single-crystal X-ray diffraction analysis.It crystallizes in triclinic system,P1 space group with a = 10.05（5） ,b = 11.53（5）,c = 12.92（6） ,α = 112.11（6）°,β = 92.79（7）°,γ = 102.98（7）°,V = 1337.113,Z = 4,Mr = 253.25,Dc = 1.258 g.cm-3,μ = 0.099 mm-1,F（000） = 536,the final R = 0.0822 and wR = 0.2575 for 1893 observed reflections（I 2σ（I））.Based on it,a two-dimensional grid-type Zn（Ⅱ） coordina-tion polymer of {[Zn（pybdc）（bpy）（H2O）].2H2O.0.5CH3OH}n（1） was solvothermally synthesized,which crystallizes in triclinic,space group P1 with a = 10.218（5） ？,b = 11.176（5） ,c =11.350（5） ,α = 95.855（5）°,β = 94.248（5）°,γ = 101.421（5）°,V = 1257.9（2） 3,Z = 2,Mr = 524.84,Dc = 1.386 g.cm-3,μ = 1.024 mm-1,F（000） = 546,the final R = 0.0635 and wR = 0.1879 for 3913 observed reflections（I 2σ（I））.展开更多
The crystal of the title compound with formula C36H44Cl2F3Mo2NO8S2 (Mr = 10002.62) crystallized in monoclinic, space group P21/n, with a = 9.6184(1), b = 22.3476(2), c = 20.7758(2) ?, ( = 90.172(1)(, V = 4465.70(7) ?3...The crystal of the title compound with formula C36H44Cl2F3Mo2NO8S2 (Mr = 10002.62) crystallized in monoclinic, space group P21/n, with a = 9.6184(1), b = 22.3476(2), c = 20.7758(2) ?, ( = 90.172(1)(, V = 4465.70(7) ?3, Z = 4, Dc = 1.491 g/cm3, F(000) = 2032, ( = 0.833 mm－1, Final R = 0.0665 and wR = 0.1650 for 5044 reflections with I >2.0( (I). The crystal structure revealed that the Mo2S2 core is planar, and the trifluoroacetic group acts as a bidentate bridging ligand and coordinates to two Mo atoms forming a five-membered ring plane, in which the Mo-Mo bond distance is 2.9222(9) ? and the O-C-O angle is 131.8(7)展开更多
The hydrothermal reaction of 5-methoxyisophthalic acid（MeO-H2ip）, 1,3-bis（2-methylimidazol-1-yl）propane（bmip） and Zn（NO3）2·6H2O in the presence of NaOCH3 gave rise to a three-dimensional（3-D） metal-orga...The hydrothermal reaction of 5-methoxyisophthalic acid（MeO-H2ip）, 1,3-bis（2-methylimidazol-1-yl）propane（bmip） and Zn（NO3）2·6H2O in the presence of NaOCH3 gave rise to a three-dimensional（3-D） metal-organic framework containing octanuclear Zn（II） units, [Zn4（MeO-ip）3（OH）2（bmip）]n. Single-crystal X-ray diffraction analysis reveals that the complex crystallizes in the triclinic space group P1 with a = 11.348（3）, b = 14.163（4）, c = 15.088（4） , α = 108.537（2）, β = 106.542（2）, γ = 103.106（1）o, V = 2065.4（9） -3, Z = 2, Mr = 334.62, Dc = 1.740 g·cm-（-3）, μ = 2.375 mm-（-1）, S = 1.015, F（000） = 1096, the final R = 0.0272 and w R = 0.0715 for 8929 observed reflections（I 〉 2σ（I））. The complex is thermally stable up to 370 oC, and exhibits photoluminescent emission at 450 nm on 350 nm excitation.展开更多
One coordination polymer with bifunctional zwitterionic ligand bearing both carboxylate and tetrazolate groups, [Cd（L1）（N3）]n·n H2O（1, L1 = 1-（carboxylatomethyl）-4-（5-tetrazolato）pyridinium], has been in...One coordination polymer with bifunctional zwitterionic ligand bearing both carboxylate and tetrazolate groups, [Cd（L1）（N3）]n·n H2O（1, L1 = 1-（carboxylatomethyl）-4-（5-tetrazolato）pyridinium], has been in situ hydrothermally synthesized and structurally characterized. Compound 1 crystallizes in monoclinic with C2/m space group, a = 21.8038（17）, b = 7.6087（6）, c = 7.8342（6） A, β = 106.166（2）o, V = 1248.29（17） A3, Z = 4, Mr = 376.62, Dc = 2.004 g·cm-3, F（000） = 736, μ = 1.772 mm-1, Rint = 0.0217, S = 1.088, the final R = 0.0415 and w R = 0.1128 for 1020 observed reflections with I 2σ（I）. The compound exhibits two-dimensional coordination sheets, in which infinite anionic [Cd（CN4）（N3）（OCO）]n chains with the tricomponent（μ-azide）（μ-tetrazolate）（μ-carboxylate） bridges are cross-linked by cationic 1-methylenepyridinium spacers of the L1 ligand. This compound in the solid state exhibits blue luminescence assignable to intraligand transitions.展开更多
The impact of alkali metal carboxylates on the synthesis of colloidal quantum dots(CQDs)was investigated.Through a ligand removal experiment,we demonstrated that due to its high hydrophilic nature,sodium oleate disper...The impact of alkali metal carboxylates on the synthesis of colloidal quantum dots(CQDs)was investigated.Through a ligand removal experiment,we demonstrated that due to its high hydrophilic nature,sodium oleate dispersed in n-octadecene(ODE)with the formation of micelles with the help of other polar molecules,which resulted in reduced concentration of oleic acid and cadmium oleate both in the solution and on the surface of CQDs.These effects allow for control the size of CdSe CQDs in a wide range when synthesizing them by solely changing the amount of sodium oleate,under either cation-rich or anion-rich conditions.Additionally,enhanced ligand dynamics promote morphology transformation and suppress size deviation caused by different morphologies'existence in CQDs synthesis.Alkali metal oleate not only stabilized anion-rich CdSe CQDs but also results in highly crystallized wurtzite structure of CdSe CQDs when synthesizing them with excess anions.Furthermore,under anion-rich synthetic condition,anisotropic growth can be realized,leading to nanorods and nanoplatelets based on the alkali metal ions used.Given their outstanding effects and widely applicable synthetic conditions,alkali metal carboxylates offer new possibilities for designing efficient methods for synthesizing CQDs.展开更多
基金supported by the National Natural Science Foundation of China(No.51563019)the Natural Science Foundation of Inner Mongolia(No.2013MS0212,2018BS02009)
文摘A new gadolinium porous complex,(NH4)2[Gd2(pzdc)4(H2O)2],was synthesized through hydrothermal reaction of 2,3-pyrazinedicarboxylic acid and Gd(NO3)3·6 H2O with the pH value adjusted by ammonia.It was characterized by elemental analysis,FT-IR,TGA and further by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group P21/c with a=14.249(7),b=15.889(8),c=12.846(7)A,β=95.724(10)°,V=2894(3)A^3,Z=4,Dc=2.385 g/cm^3,μ(Mo Ka)=4.65 mm^–1 and F(000)=1976.1976 reflections were measured and 6446 independent reflections(Rint=0.0985)were used in further refinement.The complex exhibits a 3D framework constructed from the[Gd2(pzdc)4(H2O)2]2-building blocks.It is scarce that the NH4+cations are located in the channels and balance the charge of anion framework.Furthermore,the ion exchange property of this complex has also been studied.The NH4+cations can be replaced by Na+cations,which is an uncommon phenomenon for gadolinium-containing porous complex.
基金supported by the Natural Science Foundation of Shanxi Province(No.2013011011-6)the Subject Team of Taiyuan University of Science and Technology
文摘One new mixed-ligand coordination polymer,namely[Co2（btc）（bpdc）（0.5）（py）3]n（1）,was hydrothermally synthesized using biphenyl-2,4,4＇-tricarboxylic acid（H3btc） as a main building block,along with two auxiliary ligands（H2bpdc = 2,2＇-bipyridine-5,5＇-dicarboxylic acid and py =pyridine）.The product 1 was characterized by IR spectroscopy,elemental,thermogravimetric,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction studies show that compound 1 possesses an intricate 3D metal-organic framework based on tetracobalt（Ⅱ） units.Magnetic susceptibility measurement indicates that compound 1 shows an antiferromagnetic coupling between the Co（Ⅱ） ions.
基金supported by the National Natural Science Fund for Distinguished Young Scholars of China (No 20725101)the 973 Program (No 2006CB932904)+2 种基金the NSF of Fujian Province (Nos E0510030 and 2008F3120)the Knowledge Innovation Program of CAS (No KJCX2YWH01)the NNSFC (No 20521101)
文摘Two novel lanthanide-organic polymers [Er2（pdc）2（o-bdc）（H2O）2]·H2O（1,H2pdc = 2,6-pyridinedicarboxylic acid,o-H2bdc = 1,2-benzenedicarboxylic acid） and Er（Himdc）（mbdc）0.5（H2O）（2,H3imdc = 4,5-imidazoledicarboxylic acid,m-H2bdc = 1,3-benzenedicarboxylic acid） have been synthesized and characterized by elemental analysis,IR,thermogravimetric analysis and X-ray single-crystal diffraction studies.1 crystallizes in monoclinic,space group P21/c,while 2 in the orthorhombic space group Pbcn.Both compounds 1 and 2 display two-dimensional network structures. For 1, the tetranuclear parallelogram {Era} cluster as a building block is further assembled into a wonderful 2D grid, and the layers are interconnected via hydrogen bonds and π-π stacking interactions to yield a 3D supramolecular architecture; for 2, its configuration is a rare double-decker structure. These two complexes represent good examples for using mixcarboxylate-containing ligands to construct diverse 2D lanthanide coordination polymers.
基金supported by the National Natural Science Foundation of China(No.21571118)
文摘The title Mn（Ⅱ） coordination polymer,poly{[heptaaqua-（μ4-bi-phenyl-3,3？,5,5？-tetracarboxylate）-bimanganese（Ⅱ）] pentahydrate},[Mn_2（bpta）（H_2O）_7]_n·5n H_2O（I）,is crystallized from a mixture of biphenyl-3,3？,5,5？-tetracarboxylic acid（H_4bpta） and MnCl_2·4H_2O in waterethanol under room temperature. Its asymmetric unit consists of one and two halves of crystallographically independent Mn（Ⅱ） cations,one fully deprotonated H4 bpta ligand,seven coordinated water molecules and five solvent water as guest molecules. In I,each Mn（Ⅱ） atom is octahedrally coordinated by six oxygen atoms from bpta^（4-） anions and coordinated water molecules. In the Mn（Ⅱ） cations,one half Mn（Ⅱ） ion of them located at a 2-fold axis generating a trinuclear [Mn_3（H_2O）_2（RCOO）_2] linker by μ1,1-O（water） and μ1,3-O,O？（carboxylate） bridges and another half Mn（Ⅱ） ion with an inversion is a mononuclear linker. These neighbouring trinuclear and mononuclear Mn（Ⅱ） cations are linked together by biphenyl-3,3？,5,5？-tetracarboxylates to form a three-dimensional framework with a（42.84） topology of a（4,4）-connected net,in which the positions of the trinuclear [Mn_3（H_2O）_2（R-COO）_2] linker as a 4-connector linking four bpta^（4-） ligands in I reproduce an eagle-shaped arrangement. The polymeric structure exhibits a water channel with an accessible void of 797.1 ？~3,amounting to 15.7% of the total unit-cell volume. Each of the cavities in the network is occupied by solvent water molecules.
文摘The crystal of the title compound with formula C36H44Cl2F3Mo2NO8S2 (Mr = 10002.62) crystallized in monoclinic, space group P21/n, with a = 9.6184(1), b = 22.3476(2), c = 20.7758(2) ?, ( = 90.172(1)(, V = 4465.70(7) ?3, Z = 4, Dc = 1.491 g/cm3, F(000) = 2032, ( = 0.833 mm－1, Final R = 0.0665 and wR = 0.1650 for 5044 reflections with I >2.0( (I). The crystal structure revealed that the Mo2S2 core is planar, and the trifluoroacetic group acts as a bidentate bridging ligand and coordinates to two Mo atoms forming a five-membered ring plane, in which the Mo-Mo bond distance is 2.9222(9) ? and the O-C-O angle is 131.8(7)
基金supported by the Natural Science Foundation of Fujian Province(2015J01038)Provincial Education Department of Fujian(JA12070)State Key Laboratory of Structural Chemistry(20150015)
文摘The hydrothermal reaction of 5-methoxyisophthalic acid（MeO-H2ip）, 1,3-bis（2-methylimidazol-1-yl）propane（bmip） and Zn（NO3）2·6H2O in the presence of NaOCH3 gave rise to a three-dimensional（3-D） metal-organic framework containing octanuclear Zn（II） units, [Zn4（MeO-ip）3（OH）2（bmip）]n. Single-crystal X-ray diffraction analysis reveals that the complex crystallizes in the triclinic space group P1 with a = 11.348（3）, b = 14.163（4）, c = 15.088（4） , α = 108.537（2）, β = 106.542（2）, γ = 103.106（1）o, V = 2065.4（9） -3, Z = 2, Mr = 334.62, Dc = 1.740 g·cm-（-3）, μ = 2.375 mm-（-1）, S = 1.015, F（000） = 1096, the final R = 0.0272 and w R = 0.0715 for 8929 observed reflections（I 〉 2σ（I））. The complex is thermally stable up to 370 oC, and exhibits photoluminescent emission at 450 nm on 350 nm excitation.
基金Partly supported by the Key Research Foundation of Wannan Medical College(WK2014Z06)Doctoral Starting up Foundation of Wannan Medical College(201219)the Foundation of Science and Technology Development of Shanghai(14ZR1447900)
文摘One coordination polymer with bifunctional zwitterionic ligand bearing both carboxylate and tetrazolate groups, [Cd（L1）（N3）]n·n H2O（1, L1 = 1-（carboxylatomethyl）-4-（5-tetrazolato）pyridinium], has been in situ hydrothermally synthesized and structurally characterized. Compound 1 crystallizes in monoclinic with C2/m space group, a = 21.8038（17）, b = 7.6087（6）, c = 7.8342（6） A, β = 106.166（2）o, V = 1248.29（17） A3, Z = 4, Mr = 376.62, Dc = 2.004 g·cm-3, F（000） = 736, μ = 1.772 mm-1, Rint = 0.0217, S = 1.088, the final R = 0.0415 and w R = 0.1128 for 1020 observed reflections with I 2σ（I）. The compound exhibits two-dimensional coordination sheets, in which infinite anionic [Cd（CN4）（N3）（OCO）]n chains with the tricomponent（μ-azide）（μ-tetrazolate）（μ-carboxylate） bridges are cross-linked by cationic 1-methylenepyridinium spacers of the L1 ligand. This compound in the solid state exhibits blue luminescence assignable to intraligand transitions.
基金supported by the Shanghai Rising-Star Program(No.22QA1406300)the National Natural Science Foundation of China(No.U22A2072)the Start-up Funding of ShanghaiTech University.
文摘The impact of alkali metal carboxylates on the synthesis of colloidal quantum dots(CQDs)was investigated.Through a ligand removal experiment,we demonstrated that due to its high hydrophilic nature,sodium oleate dispersed in n-octadecene(ODE)with the formation of micelles with the help of other polar molecules,which resulted in reduced concentration of oleic acid and cadmium oleate both in the solution and on the surface of CQDs.These effects allow for control the size of CdSe CQDs in a wide range when synthesizing them by solely changing the amount of sodium oleate,under either cation-rich or anion-rich conditions.Additionally,enhanced ligand dynamics promote morphology transformation and suppress size deviation caused by different morphologies'existence in CQDs synthesis.Alkali metal oleate not only stabilized anion-rich CdSe CQDs but also results in highly crystallized wurtzite structure of CdSe CQDs when synthesizing them with excess anions.Furthermore,under anion-rich synthetic condition,anisotropic growth can be realized,leading to nanorods and nanoplatelets based on the alkali metal ions used.Given their outstanding effects and widely applicable synthetic conditions,alkali metal carboxylates offer new possibilities for designing efficient methods for synthesizing CQDs.
