Synthesizing zirconium-oxo clusters(ZrOCs)with precisely defined“mother-daughter”architectures(large clusters containing smaller cluster units)is essential for gaining a profound understanding of their assembly mech...Synthesizing zirconium-oxo clusters(ZrOCs)with precisely defined“mother-daughter”architectures(large clusters containing smaller cluster units)is essential for gaining a profound understanding of their assembly mechanism and precisely controlling their properties.However,owing to considerable synthetic difficulties,achieving this goal remains a formidable challenge.Herein,we report the synthesis of two novel high-nuclearity ZrOCs,namely[Zr_(16)(μ_(3)-O/OH)_(24)(μ_(2)-OH)_(4)(QE)_(4)(PA)_(20)](Zr_(16);H_(2)QE=2,8-quinolinediol;HPA=propanoic acid)and[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(PA)_(20)](Zr20),via a facile solvent-induced synthetic strategy.Surprisingly,we found that Zr16 and Zr20 exhibit a“mother-daughter”relationship,where Zr16,as the“daughter”,is embedded within Zr20,the“mother”,with the PA ligands excluded.Moreover,Zr20 can react with benzoic acid(HBA)via post-synthetic reactions to yield another new cluster,[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(BA)_(20)](Zr20-BA),which retains the metal core and QE ligands of Zr20,with only the peripheral PA ligands replaced by BA ligands,highlighting the framework stability and flexibility of ligand shell of Zr20.Of note,Zr20 exhibited better thermal catalytic cycloaddition of CO_(2)and epoxides performance due to the rich Lewis acidity of Zr sites,achieving near-complete conversion of diverse epoxides.This work not only expands the structural landscape of high-nuclearity Zr OCs but also provides deeper insights into their underlying assembly mechanism.展开更多
A high-nuclear Co-V-O cluster was firstly isolated by lacunary polyoxoanion, resulting in the high-nuclear mixed metal-oxo cluster-containing polyoxometalate (POM), K4Na28[{Co4(O-H)3(VO4)}4(SiW9O34)4]· 66H2O (1)....A high-nuclear Co-V-O cluster was firstly isolated by lacunary polyoxoanion, resulting in the high-nuclear mixed metal-oxo cluster-containing polyoxometalate (POM), K4Na28[{Co4(O-H)3(VO4)}4(SiW9O34)4]· 66H2O (1). In 1, the{Co4(O-H)3(VO4)}4{Co16-V4}core, composed of a{Co4O4}cubane, four{Co4(OH)3}qusi-cubanes and four VO4 units, was stabilized by four lacunary A-α-{SiW9O34} units. Photocatalytic study reveals that 1 exhibits excellent photocatalytic activity for CO2-to-CO conversion with high selectivity under visible light irradiation. The turnover number (TON) and turnover frequency (TOF) reaches as high as 10492 and 0.29 s^-1, respectively. Compound 1 represents the first high nuclear TM cluster-containing POM (TM=transition-metal) with efficient visible light catalytic activity for CO2 reduction, and its photocatalytic activity is much higher than those of most reported molecular catalysts. Photoluminescence spectroscopy study reveals that photoexcitation of Ru-photosensitizer is followed by an efficient electron transfer to POMs to reduce CO2.展开更多
The design of assembling high-nuclearity transition-lanthanide(3d-4f) clusters along with excellent magnetocaloric effect(MCE) is one of the most prominent fields but is extremely challenging. Herein, two heterometall...The design of assembling high-nuclearity transition-lanthanide(3d-4f) clusters along with excellent magnetocaloric effect(MCE) is one of the most prominent fields but is extremely challenging. Herein, two heterometallic metal coordination polymers are constructed via the “carbonatetemplate” method, formulated as {[Gd_(18)Ni_(24)(IDA)_(22)(CO_(3))_(7)(μ_(3)-OH)_(32)(μ_(2)-OH)_(3)(H_(2)O)_(5)Cl]·Cl_(8)·(H_(2)O)_(14)}nand{[Eu_(18)Ni_(23.5)(IDA)_(22)(CO_(3)_(7)(μ_(3)-OH)_(32)(H_(2)O)_(5)(IN)(CH_(3)COO)_(2)(NH_(2)CH_(2)COO)Cl]·C_(l6)·(H_(2)O)_(17)}n[abbreviated as 1-(Gd_(18)Ni_(24))nand 2-(Eu_(18)Ni_(23.5))n respectively;H_(2)IDA = iminodiacetic acid;HIN = isonicotinic acid]. Concerning the structures, compounds 1-(Gd_(18)Ni_(24))nand 2-(Eu_(18)Ni_(23.5))nboth feature the one-dimensional(1D) chain-like structure which is rarely reported in high-nuclearity metal complexes. Meanwhile, the large presences of Gd3+ ions in compound 1-(Gd18Ni24)nare conducive to the fantastic MCE, and the value of-ΔS_(m)is 35.30 J kg^(-1)K^(-1) at 3.0 K and ΔH = 7.0 T. And more significantly, compound 1-Gd_(18)Ni_(24)n shows the large low-field magnetic entropy change(-ΔS_(m)= 20.95 J kg(-1) K(-1) at 2.0 K and ΔH = 2.0 T)among the published 3 d-4 f mixed metal clusters.展开更多
A novel sodium holmium carboxylate compound,namely Na 4 Ho 4 （μ 3-OH） 4 （1,4BDC） 6 ·6.25H 2 O （1,1,4-BDC=1,4-benzenedicarboxylate）,has been solvothermally synthesized and structurally characterized.The str...A novel sodium holmium carboxylate compound,namely Na 4 Ho 4 （μ 3-OH） 4 （1,4BDC） 6 ·6.25H 2 O （1,1,4-BDC=1,4-benzenedicarboxylate）,has been solvothermally synthesized and structurally characterized.The structure features a two-fold interpenetrated three-dimensional open-framework constructed by the [Ho 4 （μ 3-OH） 4 ] 8＋ clusters bridged by 1,4-BDC ligands.The Na ＋ ions and lattice water molecules are located in the channels.The structure is further stabilized by hydrogen-bonding and π-π stacking interactions.The thermal stability of the compound has been investigated via thermogravimetric analysis.展开更多
The synergistic effect of trivacant B-α-Ge W_(9)O_(34)fragments as structure-directing agents and inorganic B-O segments as intramolecular decoration afforded an unprecedented 28-Ni-added huge cluster K_(2)Na_(14)H_(...The synergistic effect of trivacant B-α-Ge W_(9)O_(34)fragments as structure-directing agents and inorganic B-O segments as intramolecular decoration afforded an unprecedented 28-Ni-added huge cluster K_(2)Na_(14)H_(10)[{Ni_(6)(OH)_(3)(H_(2)O)_(6)(Ge W_(9)O_(34))}{Ni_(8)-(μ_(6)-O)(OH)_(3)(H_(2)O)(BO(OH)_(2))(B_(2)O_(3)(OH)_(2))(Ge W_(9)O_(34))_(2)}]_(2)·46H_(2)O(1)under hydrothermal conditions.The polyoxoanion of 1contains two half-units,[{Ni_(6)(OH)_(3)(H_(2)O)_(6)(Ge W_(9)O_(34))}{Ni_(8)(μ_(6)-O)(OH)_(3)(H_(2)O)(BO(OH)_(2))(B_(2)O_(3)(OH)_(2))(Ge W_(9)O_(34))_(2)}]^(13-),which joined together via Ni-O=W linkages.The most fascinating feature is that each half-unit can be regarded as the fusion of an Ni_(6)(OH)_(3)(H_(2)O)_(6)(B-α-Ge W_(9)O_(34))({Ni_6Ge W_(9)})and a previously unobserved sandwiched Ni_(8)(μ_(6)-O)(OH)_(3)(H_(2)O)(BO(OH)_(2))(B_(2)O_(3)-(OH)_(2))(B-α-Ge W_(9)O_(34))_(2)({(Ni_(8)BB_(2))@(Ge W_(9))_(2)}),in which the{Ni_(8)BB_(2)}cluster contains a Lindqvist-type{Ni_(6)}core capped by two Ni O_(6)octahedra and further decorated by a BO(OH)_(2)({B})group and a binuclear B_(2)O_(3)(OH)_(2)({B_(2)})cluster.Furthermore,1 as a heterogeneous catalyst,has good catalytic activity for Knoevenagel condensation under mild reaction conditions.展开更多
It is a meaningful and challenging work for structural and synthetic chemists to isolate nano-sized high-nuclearity cluster-molecules.In this work,two largest hetero-metallic nano-clusters Gd_(158)Co_(38) were obtaine...It is a meaningful and challenging work for structural and synthetic chemists to isolate nano-sized high-nuclearity cluster-molecules.In this work,two largest hetero-metallic nano-clusters Gd_(158)Co_(38) were obtained via the“multi-anions-template”method.Different from the reported giant hollow-nano-clusters,the Ln_(158) core in Gd_(158)Co_(38)(the protein-sized nano-clusters,ca.4.3 nm×3.6 nm×3.5 nm)has the highest Ln nuclear number,which is integrated by twelve halide ions(with the form of icosahedron)as key templates,while Co ions(as 3d metals)are located in its periphery.This emergence indicates a novel structure form of non-open Ln-containing high-nuclearity clusters,and affords a consummate pattern to analyse and assemble the complex cluster-molecules.In addition,Gd_(158)Co_(38)@Cl_(12)breaks the record magnetic entropy change of 3d-4f clusters with−∆S_(m)^(max)=46.95 J kg^(−1)K^(−1)at 7.0 T,2.0 K.展开更多
基金supported by the National Natural Science Foundation of China(22325105,22201159,22171164,91961105,92361301,52261135637)the Natural Science Foundation of Shandong Province(ZR2021QB077,ZR2024MB120)the Doctoral Program of Liaocheng University(318051944)。
文摘Synthesizing zirconium-oxo clusters(ZrOCs)with precisely defined“mother-daughter”architectures(large clusters containing smaller cluster units)is essential for gaining a profound understanding of their assembly mechanism and precisely controlling their properties.However,owing to considerable synthetic difficulties,achieving this goal remains a formidable challenge.Herein,we report the synthesis of two novel high-nuclearity ZrOCs,namely[Zr_(16)(μ_(3)-O/OH)_(24)(μ_(2)-OH)_(4)(QE)_(4)(PA)_(20)](Zr_(16);H_(2)QE=2,8-quinolinediol;HPA=propanoic acid)and[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(PA)_(20)](Zr20),via a facile solvent-induced synthetic strategy.Surprisingly,we found that Zr16 and Zr20 exhibit a“mother-daughter”relationship,where Zr16,as the“daughter”,is embedded within Zr20,the“mother”,with the PA ligands excluded.Moreover,Zr20 can react with benzoic acid(HBA)via post-synthetic reactions to yield another new cluster,[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(BA)_(20)](Zr20-BA),which retains the metal core and QE ligands of Zr20,with only the peripheral PA ligands replaced by BA ligands,highlighting the framework stability and flexibility of ligand shell of Zr20.Of note,Zr20 exhibited better thermal catalytic cycloaddition of CO_(2)and epoxides performance due to the rich Lewis acidity of Zr sites,achieving near-complete conversion of diverse epoxides.This work not only expands the structural landscape of high-nuclearity Zr OCs but also provides deeper insights into their underlying assembly mechanism.
基金financial support from Science and Technology Research Foundation of the Thirteenth Five Years of Jilin Educational Committee (No. JJKH20170605KJ)
文摘A high-nuclear Co-V-O cluster was firstly isolated by lacunary polyoxoanion, resulting in the high-nuclear mixed metal-oxo cluster-containing polyoxometalate (POM), K4Na28[{Co4(O-H)3(VO4)}4(SiW9O34)4]· 66H2O (1). In 1, the{Co4(O-H)3(VO4)}4{Co16-V4}core, composed of a{Co4O4}cubane, four{Co4(OH)3}qusi-cubanes and four VO4 units, was stabilized by four lacunary A-α-{SiW9O34} units. Photocatalytic study reveals that 1 exhibits excellent photocatalytic activity for CO2-to-CO conversion with high selectivity under visible light irradiation. The turnover number (TON) and turnover frequency (TOF) reaches as high as 10492 and 0.29 s^-1, respectively. Compound 1 represents the first high nuclear TM cluster-containing POM (TM=transition-metal) with efficient visible light catalytic activity for CO2 reduction, and its photocatalytic activity is much higher than those of most reported molecular catalysts. Photoluminescence spectroscopy study reveals that photoexcitation of Ru-photosensitizer is followed by an efficient electron transfer to POMs to reduce CO2.
基金supported by the Natural Science Foundation of China (No. 21571103)Jiangsu (No. BK20191359)the Project of Natural Science Foundation of the Higher Education Institutions of Anhui Province, China (No. KJ2019A0350)。
文摘The design of assembling high-nuclearity transition-lanthanide(3d-4f) clusters along with excellent magnetocaloric effect(MCE) is one of the most prominent fields but is extremely challenging. Herein, two heterometallic metal coordination polymers are constructed via the “carbonatetemplate” method, formulated as {[Gd_(18)Ni_(24)(IDA)_(22)(CO_(3))_(7)(μ_(3)-OH)_(32)(μ_(2)-OH)_(3)(H_(2)O)_(5)Cl]·Cl_(8)·(H_(2)O)_(14)}nand{[Eu_(18)Ni_(23.5)(IDA)_(22)(CO_(3)_(7)(μ_(3)-OH)_(32)(H_(2)O)_(5)(IN)(CH_(3)COO)_(2)(NH_(2)CH_(2)COO)Cl]·C_(l6)·(H_(2)O)_(17)}n[abbreviated as 1-(Gd_(18)Ni_(24))nand 2-(Eu_(18)Ni_(23.5))n respectively;H_(2)IDA = iminodiacetic acid;HIN = isonicotinic acid]. Concerning the structures, compounds 1-(Gd_(18)Ni_(24))nand 2-(Eu_(18)Ni_(23.5))nboth feature the one-dimensional(1D) chain-like structure which is rarely reported in high-nuclearity metal complexes. Meanwhile, the large presences of Gd3+ ions in compound 1-(Gd18Ni24)nare conducive to the fantastic MCE, and the value of-ΔS_(m)is 35.30 J kg^(-1)K^(-1) at 3.0 K and ΔH = 7.0 T. And more significantly, compound 1-Gd_(18)Ni_(24)n shows the large low-field magnetic entropy change(-ΔS_(m)= 20.95 J kg(-1) K(-1) at 2.0 K and ΔH = 2.0 T)among the published 3 d-4 f mixed metal clusters.
基金supported by the NNSFC (Nos. 20771102 and 20873149)NSF of Fujian Province(No. 2008J0174 )973 Program (No. 2006CB932904)
文摘A novel sodium holmium carboxylate compound,namely Na 4 Ho 4 （μ 3-OH） 4 （1,4BDC） 6 ·6.25H 2 O （1,1,4-BDC=1,4-benzenedicarboxylate）,has been solvothermally synthesized and structurally characterized.The structure features a two-fold interpenetrated three-dimensional open-framework constructed by the [Ho 4 （μ 3-OH） 4 ] 8＋ clusters bridged by 1,4-BDC ligands.The Na ＋ ions and lattice water molecules are located in the channels.The structure is further stabilized by hydrogen-bonding and π-π stacking interactions.The thermal stability of the compound has been investigated via thermogravimetric analysis.
基金supported by the National Natural Science Foundation of China(NSFC,21831001,21571016,91122028)the NSFC for Distinguished Young scholars(20725101)。
文摘The synergistic effect of trivacant B-α-Ge W_(9)O_(34)fragments as structure-directing agents and inorganic B-O segments as intramolecular decoration afforded an unprecedented 28-Ni-added huge cluster K_(2)Na_(14)H_(10)[{Ni_(6)(OH)_(3)(H_(2)O)_(6)(Ge W_(9)O_(34))}{Ni_(8)-(μ_(6)-O)(OH)_(3)(H_(2)O)(BO(OH)_(2))(B_(2)O_(3)(OH)_(2))(Ge W_(9)O_(34))_(2)}]_(2)·46H_(2)O(1)under hydrothermal conditions.The polyoxoanion of 1contains two half-units,[{Ni_(6)(OH)_(3)(H_(2)O)_(6)(Ge W_(9)O_(34))}{Ni_(8)(μ_(6)-O)(OH)_(3)(H_(2)O)(BO(OH)_(2))(B_(2)O_(3)(OH)_(2))(Ge W_(9)O_(34))_(2)}]^(13-),which joined together via Ni-O=W linkages.The most fascinating feature is that each half-unit can be regarded as the fusion of an Ni_(6)(OH)_(3)(H_(2)O)_(6)(B-α-Ge W_(9)O_(34))({Ni_6Ge W_(9)})and a previously unobserved sandwiched Ni_(8)(μ_(6)-O)(OH)_(3)(H_(2)O)(BO(OH)_(2))(B_(2)O_(3)-(OH)_(2))(B-α-Ge W_(9)O_(34))_(2)({(Ni_(8)BB_(2))@(Ge W_(9))_(2)}),in which the{Ni_(8)BB_(2)}cluster contains a Lindqvist-type{Ni_(6)}core capped by two Ni O_(6)octahedra and further decorated by a BO(OH)_(2)({B})group and a binuclear B_(2)O_(3)(OH)_(2)({B_(2)})cluster.Furthermore,1 as a heterogeneous catalyst,has good catalytic activity for Knoevenagel condensation under mild reaction conditions.
基金supported by the National Key R&D Program of China(2018YFA0306004)the National Natural Science Foundation of China(21571103,21973038)+1 种基金Jiangsu Province(BK20191359)the Joint Fund for Regional Innovation and Development(U20A2073)。
文摘It is a meaningful and challenging work for structural and synthetic chemists to isolate nano-sized high-nuclearity cluster-molecules.In this work,two largest hetero-metallic nano-clusters Gd_(158)Co_(38) were obtained via the“multi-anions-template”method.Different from the reported giant hollow-nano-clusters,the Ln_(158) core in Gd_(158)Co_(38)(the protein-sized nano-clusters,ca.4.3 nm×3.6 nm×3.5 nm)has the highest Ln nuclear number,which is integrated by twelve halide ions(with the form of icosahedron)as key templates,while Co ions(as 3d metals)are located in its periphery.This emergence indicates a novel structure form of non-open Ln-containing high-nuclearity clusters,and affords a consummate pattern to analyse and assemble the complex cluster-molecules.In addition,Gd_(158)Co_(38)@Cl_(12)breaks the record magnetic entropy change of 3d-4f clusters with−∆S_(m)^(max)=46.95 J kg^(−1)K^(−1)at 7.0 T,2.0 K.
