A new hexanuclear silver（I） compound containing thiosemicarbazone with group of 3-pyridine was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spect...A new hexanuclear silver（I） compound containing thiosemicarbazone with group of 3-pyridine was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound 3 crystallizes in monoclinic,space group C2/m with a = 18.6523（9）,b = 24.7519（11）,c = 22.4542（15） ,β = 93.4960（10）°,V = 10347.4（10）3,C68H104Ag6N30O8S6,Mr = 2309.39,Dc = 1.482g/cm3,μ（MoKα） = 1.293 mm-1,F（000） = 4656,Z = 4,the final R = 0.0544 and wR = 0.1580 for 6733 observed reflections（I 〉 2σ（I））.In the structure,two Ag6L36（L3 = pyridine-3-carboxaldehyde thiosemicarbazone） clusters are contained.In each cluster,the S atom of ligand L3 served as a triply bridged chelator to connect the six silver atoms into a Ag6L36 cluster.Luminescence investigation revealed that the band at 630 nm was attributed to cluster-centered（CC） electron transfer,and those at 493 and 530 nm to the LMCT and CC transitions,respectively.展开更多
A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and st...A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489（4）,b=14.234（5）,c=14.484（5）,α=82.848（4）,β=79.399（4）,γ=73.646（4）°,V=2421.2（13） 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F（000）=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I 2σ（Ⅰ）.In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.展开更多
A new hexanuclear silver （I） compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence ...A new hexanuclear silver （I） compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in triclinic, space group P with a = 11.611（3）, b = 15.610（5）, c = 15.624（7） , α = 113.942（6）, β = 104.520（6）, γ = 104.230（4）°, V = 2304.1（14） 3, C60H77Ag6N22O4.5S6, Mr = 2018.02, Dc = 1.454 g/cm3, μ（MoKα） = 1.435 mm-1, F（000） = 1005, Z = 1, the final R = 0.0468 and wR = 0.1474 for 6608 observed reflections （I 2σ（I））. In the structure, the S atom of the ligand L2 （L2 = benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L26 cluster. The luminescence property of compound 2 was investigated at room temperature.展开更多
A new hexanuclear silver（I） compound containing thiosemicarbazones with groups of 1-naphthalene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence...A new hexanuclear silver（I） compound containing thiosemicarbazones with groups of 1-naphthalene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in monoclinic, space group P21/c with a = 16.101（4）, b = 24.855（7）, c = 14.492（4） A, β = 109.730（5）, V = 5459（3） A3, C90H102Ag6N2406S6, Mr= 2455.54, Dc= 1.494 g/cm3,μ（MoKa） = 1.228 mm^-1, F（000） = 2472, Z = 2, the final R = 0.0761 and wR = 0.1507 for 5258 observed reflections （I〉 2α（I））. In the structure, the S atom of ligand L serves as a triply bridged chelator to connect the six silver atoms into a Ag6L6 cluster. Luminescence investigation reveals that the compound exhibits two ligand-independent cluster-centered electron transfer bands and one ligand-dependent charge transfer band.展开更多
A new silver（Ⅰ） compound 6 （[Ag6L66]·4DMF） containing thiosemicarbazone with the group of 2-chloro-1-benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental anal...A new silver（Ⅰ） compound 6 （[Ag6L66]·4DMF） containing thiosemicarbazone with the group of 2-chloro-1-benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound 6 crystallizes in monoclinic, space group C2/c with a = 26.9236（18）, b = 15.2553（8）, c = 24.6237（13） , β = 103.0680（10）°, V = 9851.7（10）3, C58H66Ag6Cl6N20O3S6, Mr = 2143.59, Dc = 1.445 g/cm3, μ（MoKα） = 1.503 mm-1, F（000） = 4232, Z = 4, the final R = 0.0565 and wR = 0.1654 for 5831 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Similar to the structure of the compounds we have reported, compound 6 also exhibits a hexanuclear silver（Ⅰ） cluster. In the cluster, the S atom of ligand L6 （L6 = 2-chloro-1-benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L66 cluster. The luminescence property of compound 6 was investigated at room temperature and compared with other similar compounds in order to find the factors influencing their luminescent property.展开更多
Photosynthesis in nature has been deemed as the most significant biochemical reaction,which maintains a relatively stable content of O_(2) and CO_(2) in the atmosphere.Herein,for a deeper comprehension of natural phot...Photosynthesis in nature has been deemed as the most significant biochemical reaction,which maintains a relatively stable content of O_(2) and CO_(2) in the atmosphere.Herein,for a deeper comprehension of natural photosynthesis,an artificial photosynthesis model reaction of photochemical CO_(2) to CO conversion(CO_(2)+2 H^(+)+2e^(-)→CO+H_(2)O)catalyzed by a homogeneous hexanuclear ring cobalt complex{K_(2)[CoO_(3)PCH_(2)N(CH_(2)CO_(2))_(2)]}_(6)(Co6 complex)is developed.Using the[Ru(bpy)_(3)]^(2+)as a photosensitizer and TEOA as a sacrificial electron donor,an optimal turnover frequency of 503.3 h^(‒1) and an apparent quantum efficiency of 0.81%are obtained.The good photocatalytic CO_(2) reduction performance is attributed to the efficient electron transfer between Co6 complex and[Ru(bpy)_(3)]^(2+),which boosts the photogenerated carriers separation of the photosensitizer.It is confirmed by the j‐V curves,light‐assisted UV‐vis curves,steady‐state photoluminescence spectra and real‐time laser flash photolysis experiments.In addition,the proposed catalytic mechanism for CO_(2) reduction reaction catalyzed by the Co6 complex is explored by the potassium thiocyanate poison experiment,Pourbaix diagram and density functional theory calculations.展开更多
The reported X-ray structure and magnetochemical properties of [Mn6O2 (OCPh)10, (CH3CN)4], effectively derived from [NBu4][Mn4O2(O2CPh)9 (H2O)] with equivalent of tren in CH3CN is shown.
The title complex 1,[Cd 4 Cu 2 （pdc） 4 （H 2 O） 14 ] （H 3 pdc=3,5-pyrazoledicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crysta...The title complex 1,[Cd 4 Cu 2 （pdc） 4 （H 2 O） 14 ] （H 3 pdc=3,5-pyrazoledicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235（10）,b=1.27935（18）,c=1.28569（17） nm,α=112.633（2）,β=102.971（3）,γ=97.089（2）o,V=0.9673（2） nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ（MoKα）=3.356 mm 1,F（000）=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I 2σ（Ⅰ）.In 1,two deprotonated 3,5-pyrazoledicarboxylic acids （pdc 3）,one copper（Ⅱ） ion and one cadmium（Ⅱ） ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium（Ⅱ） ions through chelating carboxylate groups to construct the copper（Ⅱ）-cadmium（Ⅱ） heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional （3D） supramolecular framework.展开更多
A new silver（Ⅰ） compound 4 containing thiosemicarbazone with group 2-quinoline was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. Compo...A new silver（Ⅰ） compound 4 containing thiosemicarbazone with group 2-quinoline was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. Compound 4 crystallizes in triclinic, space group P1 with a = 12.2710（9）, b = 16.9281（13）, c = 17.2984（13）, α = 112.8500（10）, β = 103.4890（10）, γ = 102.6860（10）°, V = 3020.9（4） 3, C80H94Ag6N28O6S6, Mr = 2383.41, Dc = 1.310 g/cm3, μ（MoKα） = 1.108 mm-1, F（000） = 1196, Z = 1, the final R = 0.0567 and wR = 0.1368 for 5112 observed reflections （I 〉 2σ（I））. Similar to the structure of compound 2 we have reported, compound 4 also exhibits a hexanuclear silver（Ⅰ） cluster. In the cluster, the S atom of ligand L4 （L4 = 2-quinolinecarboxaldehyde thiosemicarbazone） serves as a triply bridged chelator to connect the six silver atoms into a Ag6L46 cluster. The luminescence property of 4 is investigated at room temperature and compared with that of 2.展开更多
Compound[(n-C4H9)4N]3 [Mo6O18(N2C6H4-pNO2)] crystallizes in the orthorhombic space grou Pnma with a= 23. 964(9).b=16.948(4),c=17.968(7) A,V=7298(7) A3,Z=4,and Dc=1.58 g/cm-3. Structure solution and refinement based on...Compound[(n-C4H9)4N]3 [Mo6O18(N2C6H4-pNO2)] crystallizes in the orthorhombic space grou Pnma with a= 23. 964(9).b=16.948(4),c=17.968(7) A,V=7298(7) A3,Z=4,and Dc=1.58 g/cm-3. Structure solution and refinement based on 3113 reflections with I>3.0σ(I) gave final residuals of R= 0.072 and Rω=0.099.The anion is a substitution isopolymolybdate.展开更多
The cube is the only regular hexahedron among the Platonic solids,but supramolecules with a cubic configuration have rarely been reported.Herein,two isostructural metal–organic cubes VMOC-6 and VMOC-7 with large cavi...The cube is the only regular hexahedron among the Platonic solids,but supramolecules with a cubic configuration have rarely been reported.Herein,two isostructural metal–organic cubes VMOC-6 and VMOC-7 with large cavities are successfully synthesized by face-directed self-assembly of concave hexanuclear vanadium clusters[V_(6)O_(6)(OCH_(3))_(9)(XO_(4))(COO)_(3)]^(n−)(X=S,n=2;X=V,n=1)and large-size nitrogen-containing tetravalent ligands.VMOC-6 and VMOC-7 are the largest metal–organic cubes based on metal clusters with an outer diameter of 28.47×28.17×28.44Å^(3) and an inner cavity volume of 7785.657Å^(3).Moreover,the cages can capture volatile iodine vapor with an uptake value of up to 1.83 g g^(−1),which is superior to those of most metal–organic materials.Mechanistic studies have shown that their good adsorption capacity is closely related to the presence of large internal cavities,electron-donating pyridine groups and redox-active V sites.The present work shows the potential application of these mesoporous MOPs in the treatment of iodine-containing nuclear waste.展开更多
The directed and controllable synthesis of lanthanide clusters with precise structures has received considerable research attention,however,progress in such remains sluggish.The steps performed in a reaction system un...The directed and controllable synthesis of lanthanide clusters with precise structures has received considerable research attention,however,progress in such remains sluggish.The steps performed in a reaction system under“black-box”conditions are unpredictable and have very low controllability.The precise customization of lanthanide clusters with the same number of cores but different arrangements is particularly difficult.Using bis-acylhydrazone-derived multidentate chelating ligands with different substituents,differentially arranged hexanuclear lanthanide clusters(Dy_(6)and HNP-Dy_(6))with identical core connections but different template-motif arrangements were constructed herein for the first time using a multidentate chelating coordination method.Specifically,Dy_(6)with face-to-face and dislocation-arrangement template motifs was obtained using-N(Et)_(2)-substituted bis-acylhydrazone ligands with a strong steric hindrance effect.Changing-N(Et)_(2)to a benzene ring with a strong π-π interaction yielded HNP-Dy_(6)with inverted and coplanar arrangements of template motifs.The controllable construction of these two hexanuclear dysprosium clusters represented great progress in the precise synthesis of lanthanide clusters.High-resolution electrospray ionization-mass spectrometry(HRESI-MS)with different ionsource energies demonstrated the high stabilities of Dy_(6)and HNP-Dy_(6)in solutions.Time-dependent HRESI-MS tracked the formation processes of Dy_(6)and HNP-Dy_(6)and led to the following possible selfassembly mechanisms:L^(1)+2Dy→Dy_(2)L^(1)→Dy_(3)L^(1)→Dy_(6)(L^(1))_(2) and L^(2)+2Dy→Dy_(2)L^(2)→Dy_(3)L^(2)→Dy5(L^(2))_(2)/Dy_(6)(L^(2))_(2)→Dy_(6)(L^(2))_(2).At 1-T magnetic field,the longitudinal and transverse relaxation rates of Gd6 were 12.06 and 24.10 mM^(−1)s^(−1),respectively.Gd6 with highly aggregated Gd(Ⅲ)exhibited high relaxation rates,indicating its great potential as a T1-weighted magnetic resonance imaging contrast agent.This work provides an example of the design and synthesis of lanthanide clusters with high stabilities and relaxation rates,taking a big step toward the precise and controllable synthesis of lanthanide clusters.展开更多
Four isostructural M^(Ⅲ)_(4) Ln^(Ⅲ)_(2) coordination clusters,[M_(4)Ln_(2)(μ_(3)-OH)_(2)(nbdea)_(4)(C_(6)H_(5)COO)_(8)]·MeCN (M=Fe,Ln=Er (1);M=Ga,Ln=Er (2);M=Fe,Ln=Ho (3);M=Ga,Ln=Ho (4)) have been synthesized ...Four isostructural M^(Ⅲ)_(4) Ln^(Ⅲ)_(2) coordination clusters,[M_(4)Ln_(2)(μ_(3)-OH)_(2)(nbdea)_(4)(C_(6)H_(5)COO)_(8)]·MeCN (M=Fe,Ln=Er (1);M=Ga,Ln=Er (2);M=Fe,Ln=Ho (3);M=Ga,Ln=Ho (4)) have been synthesized and characterized. Single-crystal X-ray diffraction and X-ray powder diffraction studies revealed that all four compounds crystallize isomorphously to each other,and to the previously reported M_(4)^(Ⅲ) Dy_(2)^(Ⅲ) (M=Fe or Ga) and Fe_(4)^(Ⅲ) Y_(2)^(Ⅲ) analogues. DC magnetic susceptibility measurements for compounds 1–4,taken in combination with those for the Fe^(Ⅲ)_(4) Y^(Ⅲ)_(2) analogue,indicated that the interactions between Er^(Ⅲ) ions are weakly ferromagnetic and the Fe^(Ⅲ)–Er^(Ⅲ) interactions are very weakly antiferromagnetic,while the Ho^(Ⅲ)–Ho^(Ⅲ) and Fe^(Ⅲ)–Ho^(Ⅲ) interactions are both negligible. By comparison,for the Fe^(Ⅲ)_(4) Dy^(Ⅲ)_(2) analogue,the Dy^(Ⅲ)–Dy^(Ⅲ) interactions are antiferromagnetic while the Fe^(Ⅲ)–Dy^(Ⅲ) are ferromagnetic. Both Er analogues 1 and 2 display single-molecule magnet (SMM) behavior with the effective energy barrier Ueff increasing from 12.8 K (for Fe_(4)Er_(2) 1) to 53.5 K (for Ga_(4)Er_(2) 2),indicating that the very weak 3d–4f interaction enhances the QTM effect.展开更多
The synthesis,characterisation and capability to selectively detect vapours of volatile organic compounds(VOCs)and nitroaromatic explosives of a new family of 2-dimensional rare earth(RE)MOFs based on a hexanuclear(RE...The synthesis,characterisation and capability to selectively detect vapours of volatile organic compounds(VOCs)and nitroaromatic explosives of a new family of 2-dimensional rare earth(RE)MOFs based on a hexanuclear(RE^(3+))6 secondary building unit(SBU)is reported.The reaction of RE(NO_(3))_(3)with 4,4’-sulfonyldibenzoic acid(H_(2)SDBA)in the presence of 2-fluorobenzoic acid(HFBA)in DMF/MeOH at 100℃afforded compound[RE6(μ_(3)-OH/F)_(8)(SDBA)4(NO_(3))2(H_(2)O)_(6)]_(n)(UCY-15(RE);RE:Y,Eu,Gd,Tb,Dy,Ho,Er).展开更多
One hexanuclear cobalt cluster [Co_(2) ^(Ⅲ)Co_(4) ^(Ⅱ)(L)_(4)(CH_(3) COO)_(2)(MeO)_(4)]·MeOH(1) was synthesized by the reaction of H_(2)L(H_(2)L=2-((2-hydroxy-4-methoxy-benzylideneamino)methyl)phenol) and Co(OA...One hexanuclear cobalt cluster [Co_(2) ^(Ⅲ)Co_(4) ^(Ⅱ)(L)_(4)(CH_(3) COO)_(2)(MeO)_(4)]·MeOH(1) was synthesized by the reaction of H_(2)L(H_(2)L=2-((2-hydroxy-4-methoxy-benzylideneamino)methyl)phenol) and Co(OAc)2·4 H2O in MeOH under solvothermal conditions. Complex 1 crystalizes in the triclinic space group P1 with a = 14.397(3), b = 16.625(3), c = 18.992(4) A, α = 109.47(3)°, β = 99.24(3)°, γ = 112.37(3)°, Dc = 1.464 g/cm^(3), Z = 2, V = 3741.7(2) A^(3), the final R = 0.0781 and w R = 0.1436 for 13051 observed reflections with I > 2σ(I). In the structure of 1, two cobalt ions are in 3+ oxidation states and four cobalt ions are in 2+ valence states. The six cobalt atoms are held together by six phenolate oxygen atoms from four L^(2–) ligands, four oxygen atoms from two chelating acetates and four μ3-O atoms from four Me O– groups. The six cobalt atoms are located at six corners of four defective cubanes. Thus, complex 1 displays tetracubane-like topology. Solid-state dc magnetic susceptibilities were measured for 1 in the 2.0~300 K range. Antiferromagnetic interactions were determined for 1.展开更多
Postsynthesis of the paramagnetic square-shaped complex{[(Tp*Me)Fe(μ-CN)_(2)(CN)][Co(dmbpy)_(2)]}_(2)(BPh_(4))_(2)·6MeCN·H2O[1,Tp*Me=tris(3,4,5-trimethylpyrazole)-borate;dmbpy=4,4′-dimethyl-2,2′-bipyridin...Postsynthesis of the paramagnetic square-shaped complex{[(Tp*Me)Fe(μ-CN)_(2)(CN)][Co(dmbpy)_(2)]}_(2)(BPh_(4))_(2)·6MeCN·H2O[1,Tp*Me=tris(3,4,5-trimethylpyrazole)-borate;dmbpy=4,4′-dimethyl-2,2′-bipyridine)]by grafting transition metal(II)thiocyanates via its terminal cyano groups afforded three hexanuclear[Fe_(2)Co_(2)M_(2)]clusters(M=Zn,2;Co,3;Cd,4).The peripheral metal-complex units serving as excellent electron acceptors were found to help stabilize the low-temperature state of Fe^(II,LS)–Co^(III,LS) within the complex core.展开更多
A hexanuclear copper（Ⅰ） cluster [Cu6(C5H4NS)6] was synthesized by means of the hydrothermal reaction of [Cu(PPh3)2（MeCN）2]ClO4 with（2-mercaptopyridine-1-oxide） in the presence of 2-butanol,Et3N and water and ch...A hexanuclear copper（Ⅰ） cluster [Cu6(C5H4NS)6] was synthesized by means of the hydrothermal reaction of [Cu(PPh3)2（MeCN）2]ClO4 with（2-mercaptopyridine-1-oxide） in the presence of 2-butanol,Et3N and water and characterized by elemental analysis,IR,TGA and solid state fluorescence spectroscopy as well as X-ray diffractometry.The crystallographic data for the title complex,C15H12Cu3N3S3,are Mr=521.08,monoclinic space group P2（1）/n and the cell parameters are: a=0.958 59（6） nm,b=（1.604 85（12） nm）,（c=）0.122 712（10） nm,β=108.863（2）°,V=1.786 4（2） nm3,Z=4,Dc=（1.937 Mg/m3）,R1=0.030 1,ωR2=0.031 5（I>2σ（I））,F（000）=1 032,μ=3.890 mm-1,R（int）=0.050 1,S=0.598.The title complex exhibits highly thermal stability and strong low energy fluorescence（（λ=）744 nm） when it is irradiated by the light（λ=468 nm） in solid state at room temperature.展开更多
The integration of lanthanide(Ln)ions and polyoxoniobates(PONbs)is challenging,and the know Ln-substituted PONbs are still scarce.This work introduces high-nuclear iso-Ln-oxo clusters into th PONb system.The first ser...The integration of lanthanide(Ln)ions and polyoxoniobates(PONbs)is challenging,and the know Ln-substituted PONbs are still scarce.This work introduces high-nuclear iso-Ln-oxo clusters into th PONb system.The first series of high-nuclear Ln-oxo clusters encapsulated heterometallic polyoxonio bates H_9[Na(H_(2)O)_(4)][Cu(en)_(2)]_(10){Ln_6(μ_(3)-OH)_6(Si Nb_(18)O_(54))_(3)}·18H_(2)O(1-Ln,en=ethylenediamine,Ln=Dy,Gd Tb,Ho,Er,Tm,Yb,Lu)based on flower-like{Ln_(6)(μ_(3)-OH)_(6)(Si Nb_(18)O_(54))_(3)}({Ln_6Si_(3)Nb_(54)})clusters hav been successfully synthesized via one-pot hydrothermal synthesis strategy.The flower-like polyoxoanio{Ln_6Si_(3)Nb_(54)}is consisted of three heteropolyoxoniobate{Si Nb_(18)O_(54)}clusters and one unique planar equ lateral triangle-shaped{Ln_6(μ_(3)-OH)_6}cluster,which presents the highest nuclear iso-Ln-oxo cluster i PONb chemistry.In{Ln_6(μ_(3)-OH)_6}cluster,each pair ofμ_(3)-OH groups link three Dy^(3+)ions to form a sma approximate equilateral triangle-shaped{Dy_(3)(OH)_(2)}cluster.Furthermore,the three{Dy_(3)(OH)_(2)}cluster comprise a bigger approximate equilateral triangle-shaped{Dy_6(μ_(3)-OH)_6}cluster.The reported hexanu clear{Ln_6}cluster skeletons are mostly octahedral,however,such equilateral triangle-shaped skeleton o the hexanuclear Ln-oxo cluster is first observed.The 1-Dy exhibits good water vapor adsorption capacit and ferromagnetic properties.展开更多
基金supported by the Postdoctoral Science Foundation of Central South University
文摘A new hexanuclear silver（I） compound containing thiosemicarbazone with group of 3-pyridine was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound 3 crystallizes in monoclinic,space group C2/m with a = 18.6523（9）,b = 24.7519（11）,c = 22.4542（15） ,β = 93.4960（10）°,V = 10347.4（10）3,C68H104Ag6N30O8S6,Mr = 2309.39,Dc = 1.482g/cm3,μ（MoKα） = 1.293 mm-1,F（000） = 4656,Z = 4,the final R = 0.0544 and wR = 0.1580 for 6733 observed reflections（I 〉 2σ（I））.In the structure,two Ag6L36（L3 = pyridine-3-carboxaldehyde thiosemicarbazone） clusters are contained.In each cluster,the S atom of ligand L3 served as a triply bridged chelator to connect the six silver atoms into a Ag6L36 cluster.Luminescence investigation revealed that the band at 630 nm was attributed to cluster-centered（CC） electron transfer,and those at 493 and 530 nm to the LMCT and CC transitions,respectively.
基金Supported by the National Natural Science Foundation of China (No. 60978059)the Key Project of Chinese Ministry of Education (No. 210053)the Natural Science Foundation of Jilin Province (No. 20090527)
文摘A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489（4）,b=14.234（5）,c=14.484（5）,α=82.848（4）,β=79.399（4）,γ=73.646（4）°,V=2421.2（13） 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F（000）=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I 2σ（Ⅰ）.In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.
基金supported by the Postdoctoral Science Foundation of Central South University
文摘A new hexanuclear silver （I） compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in triclinic, space group P with a = 11.611（3）, b = 15.610（5）, c = 15.624（7） , α = 113.942（6）, β = 104.520（6）, γ = 104.230（4）°, V = 2304.1（14） 3, C60H77Ag6N22O4.5S6, Mr = 2018.02, Dc = 1.454 g/cm3, μ（MoKα） = 1.435 mm-1, F（000） = 1005, Z = 1, the final R = 0.0468 and wR = 0.1474 for 6608 observed reflections （I 2σ（I））. In the structure, the S atom of the ligand L2 （L2 = benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L26 cluster. The luminescence property of compound 2 was investigated at room temperature.
基金supported by the Postdoctoral Science Foundation of Central South University
文摘A new hexanuclear silver（I） compound containing thiosemicarbazones with groups of 1-naphthalene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in monoclinic, space group P21/c with a = 16.101（4）, b = 24.855（7）, c = 14.492（4） A, β = 109.730（5）, V = 5459（3） A3, C90H102Ag6N2406S6, Mr= 2455.54, Dc= 1.494 g/cm3,μ（MoKa） = 1.228 mm^-1, F（000） = 2472, Z = 2, the final R = 0.0761 and wR = 0.1507 for 5258 observed reflections （I〉 2α（I））. In the structure, the S atom of ligand L serves as a triply bridged chelator to connect the six silver atoms into a Ag6L6 cluster. Luminescence investigation reveals that the compound exhibits two ligand-independent cluster-centered electron transfer bands and one ligand-dependent charge transfer band.
基金supported by the National Science and Technology Support Program (2012BAC12B03)the Postdoctoral Science Foundation of Central South Universitythe Fundamental Research Funds for the Central Universities (No. 2012QNZT001)
文摘A new silver（Ⅰ） compound 6 （[Ag6L66]·4DMF） containing thiosemicarbazone with the group of 2-chloro-1-benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound 6 crystallizes in monoclinic, space group C2/c with a = 26.9236（18）, b = 15.2553（8）, c = 24.6237（13） , β = 103.0680（10）°, V = 9851.7（10）3, C58H66Ag6Cl6N20O3S6, Mr = 2143.59, Dc = 1.445 g/cm3, μ（MoKα） = 1.503 mm-1, F（000） = 4232, Z = 4, the final R = 0.0565 and wR = 0.1654 for 5831 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Similar to the structure of the compounds we have reported, compound 6 also exhibits a hexanuclear silver（Ⅰ） cluster. In the cluster, the S atom of ligand L6 （L6 = 2-chloro-1-benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L66 cluster. The luminescence property of compound 6 was investigated at room temperature and compared with other similar compounds in order to find the factors influencing their luminescent property.
文摘Photosynthesis in nature has been deemed as the most significant biochemical reaction,which maintains a relatively stable content of O_(2) and CO_(2) in the atmosphere.Herein,for a deeper comprehension of natural photosynthesis,an artificial photosynthesis model reaction of photochemical CO_(2) to CO conversion(CO_(2)+2 H^(+)+2e^(-)→CO+H_(2)O)catalyzed by a homogeneous hexanuclear ring cobalt complex{K_(2)[CoO_(3)PCH_(2)N(CH_(2)CO_(2))_(2)]}_(6)(Co6 complex)is developed.Using the[Ru(bpy)_(3)]^(2+)as a photosensitizer and TEOA as a sacrificial electron donor,an optimal turnover frequency of 503.3 h^(‒1) and an apparent quantum efficiency of 0.81%are obtained.The good photocatalytic CO_(2) reduction performance is attributed to the efficient electron transfer between Co6 complex and[Ru(bpy)_(3)]^(2+),which boosts the photogenerated carriers separation of the photosensitizer.It is confirmed by the j‐V curves,light‐assisted UV‐vis curves,steady‐state photoluminescence spectra and real‐time laser flash photolysis experiments.In addition,the proposed catalytic mechanism for CO_(2) reduction reaction catalyzed by the Co6 complex is explored by the potassium thiocyanate poison experiment,Pourbaix diagram and density functional theory calculations.
文摘The reported X-ray structure and magnetochemical properties of [Mn6O2 (OCPh)10, (CH3CN)4], effectively derived from [NBu4][Mn4O2(O2CPh)9 (H2O)] with equivalent of tren in CH3CN is shown.
基金Nanjing University of Posts and Telecommunications (No. NY209032)Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University),Ministry of Education,Science Foundation for Youths of Guangxi Province (No. 0991089)the Major State Basic Research Development Program of China (973 Program,No. 2009CB930600)
文摘The title complex 1,[Cd 4 Cu 2 （pdc） 4 （H 2 O） 14 ] （H 3 pdc=3,5-pyrazoledicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235（10）,b=1.27935（18）,c=1.28569（17） nm,α=112.633（2）,β=102.971（3）,γ=97.089（2）o,V=0.9673（2） nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ（MoKα）=3.356 mm 1,F（000）=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I 2σ（Ⅰ）.In 1,two deprotonated 3,5-pyrazoledicarboxylic acids （pdc 3）,one copper（Ⅱ） ion and one cadmium（Ⅱ） ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium（Ⅱ） ions through chelating carboxylate groups to construct the copper（Ⅱ）-cadmium（Ⅱ） heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional （3D） supramolecular framework.
基金the Postdoctoral Science Foundation of Central South University and the National Natural Science Foundation of China (No. 21105127)
文摘A new silver（Ⅰ） compound 4 containing thiosemicarbazone with group 2-quinoline was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. Compound 4 crystallizes in triclinic, space group P1 with a = 12.2710（9）, b = 16.9281（13）, c = 17.2984（13）, α = 112.8500（10）, β = 103.4890（10）, γ = 102.6860（10）°, V = 3020.9（4） 3, C80H94Ag6N28O6S6, Mr = 2383.41, Dc = 1.310 g/cm3, μ（MoKα） = 1.108 mm-1, F（000） = 1196, Z = 1, the final R = 0.0567 and wR = 0.1368 for 5112 observed reflections （I 〉 2σ（I））. Similar to the structure of compound 2 we have reported, compound 4 also exhibits a hexanuclear silver（Ⅰ） cluster. In the cluster, the S atom of ligand L4 （L4 = 2-quinolinecarboxaldehyde thiosemicarbazone） serves as a triply bridged chelator to connect the six silver atoms into a Ag6L46 cluster. The luminescence property of 4 is investigated at room temperature and compared with that of 2.
文摘Compound[(n-C4H9)4N]3 [Mo6O18(N2C6H4-pNO2)] crystallizes in the orthorhombic space grou Pnma with a= 23. 964(9).b=16.948(4),c=17.968(7) A,V=7298(7) A3,Z=4,and Dc=1.58 g/cm-3. Structure solution and refinement based on 3113 reflections with I>3.0σ(I) gave final residuals of R= 0.072 and Rω=0.099.The anion is a substitution isopolymolybdate.
基金financially supported by the NSFC of China(No.22271023,22175033).
文摘The cube is the only regular hexahedron among the Platonic solids,but supramolecules with a cubic configuration have rarely been reported.Herein,two isostructural metal–organic cubes VMOC-6 and VMOC-7 with large cavities are successfully synthesized by face-directed self-assembly of concave hexanuclear vanadium clusters[V_(6)O_(6)(OCH_(3))_(9)(XO_(4))(COO)_(3)]^(n−)(X=S,n=2;X=V,n=1)and large-size nitrogen-containing tetravalent ligands.VMOC-6 and VMOC-7 are the largest metal–organic cubes based on metal clusters with an outer diameter of 28.47×28.17×28.44Å^(3) and an inner cavity volume of 7785.657Å^(3).Moreover,the cages can capture volatile iodine vapor with an uptake value of up to 1.83 g g^(−1),which is superior to those of most metal–organic materials.Mechanistic studies have shown that their good adsorption capacity is closely related to the presence of large internal cavities,electron-donating pyridine groups and redox-active V sites.The present work shows the potential application of these mesoporous MOPs in the treatment of iodine-containing nuclear waste.
基金supported by the National Natural Science Foundation of China(22061005,22271068,and 22075058)the Basic Ability Improvement Project of Young and Middle-Aged Teachers in Guangxi Colleges(2022KY0573)PhD Start-up Fund of Yulin Normal University(G2022ZK08).
文摘The directed and controllable synthesis of lanthanide clusters with precise structures has received considerable research attention,however,progress in such remains sluggish.The steps performed in a reaction system under“black-box”conditions are unpredictable and have very low controllability.The precise customization of lanthanide clusters with the same number of cores but different arrangements is particularly difficult.Using bis-acylhydrazone-derived multidentate chelating ligands with different substituents,differentially arranged hexanuclear lanthanide clusters(Dy_(6)and HNP-Dy_(6))with identical core connections but different template-motif arrangements were constructed herein for the first time using a multidentate chelating coordination method.Specifically,Dy_(6)with face-to-face and dislocation-arrangement template motifs was obtained using-N(Et)_(2)-substituted bis-acylhydrazone ligands with a strong steric hindrance effect.Changing-N(Et)_(2)to a benzene ring with a strong π-π interaction yielded HNP-Dy_(6)with inverted and coplanar arrangements of template motifs.The controllable construction of these two hexanuclear dysprosium clusters represented great progress in the precise synthesis of lanthanide clusters.High-resolution electrospray ionization-mass spectrometry(HRESI-MS)with different ionsource energies demonstrated the high stabilities of Dy_(6)and HNP-Dy_(6)in solutions.Time-dependent HRESI-MS tracked the formation processes of Dy_(6)and HNP-Dy_(6)and led to the following possible selfassembly mechanisms:L^(1)+2Dy→Dy_(2)L^(1)→Dy_(3)L^(1)→Dy_(6)(L^(1))_(2) and L^(2)+2Dy→Dy_(2)L^(2)→Dy_(3)L^(2)→Dy5(L^(2))_(2)/Dy_(6)(L^(2))_(2)→Dy_(6)(L^(2))_(2).At 1-T magnetic field,the longitudinal and transverse relaxation rates of Gd6 were 12.06 and 24.10 mM^(−1)s^(−1),respectively.Gd6 with highly aggregated Gd(Ⅲ)exhibited high relaxation rates,indicating its great potential as a T1-weighted magnetic resonance imaging contrast agent.This work provides an example of the design and synthesis of lanthanide clusters with high stabilities and relaxation rates,taking a big step toward the precise and controllable synthesis of lanthanide clusters.
文摘Four isostructural M^(Ⅲ)_(4) Ln^(Ⅲ)_(2) coordination clusters,[M_(4)Ln_(2)(μ_(3)-OH)_(2)(nbdea)_(4)(C_(6)H_(5)COO)_(8)]·MeCN (M=Fe,Ln=Er (1);M=Ga,Ln=Er (2);M=Fe,Ln=Ho (3);M=Ga,Ln=Ho (4)) have been synthesized and characterized. Single-crystal X-ray diffraction and X-ray powder diffraction studies revealed that all four compounds crystallize isomorphously to each other,and to the previously reported M_(4)^(Ⅲ) Dy_(2)^(Ⅲ) (M=Fe or Ga) and Fe_(4)^(Ⅲ) Y_(2)^(Ⅲ) analogues. DC magnetic susceptibility measurements for compounds 1–4,taken in combination with those for the Fe^(Ⅲ)_(4) Y^(Ⅲ)_(2) analogue,indicated that the interactions between Er^(Ⅲ) ions are weakly ferromagnetic and the Fe^(Ⅲ)–Er^(Ⅲ) interactions are very weakly antiferromagnetic,while the Ho^(Ⅲ)–Ho^(Ⅲ) and Fe^(Ⅲ)–Ho^(Ⅲ) interactions are both negligible. By comparison,for the Fe^(Ⅲ)_(4) Dy^(Ⅲ)_(2) analogue,the Dy^(Ⅲ)–Dy^(Ⅲ) interactions are antiferromagnetic while the Fe^(Ⅲ)–Dy^(Ⅲ) are ferromagnetic. Both Er analogues 1 and 2 display single-molecule magnet (SMM) behavior with the effective energy barrier Ueff increasing from 12.8 K (for Fe_(4)Er_(2) 1) to 53.5 K (for Ga_(4)Er_(2) 2),indicating that the very weak 3d–4f interaction enhances the QTM effect.
基金funded under the M-ERA.NET Call 2019 and the Republic of Cyprus through the Research and Innovation Foundation(contract no:P2P/M-ERA.NET/0319/0005,Acronym:SALMOS)This research has been also funded by the Spanish AEI/MCIN/10.13039/501100011033 within the NextGenerationEU/PRTR funds through the projects PCI2020-112241(M-ERA.NET 2019 project7106,SALMOS)and PID2019-110430 GB-C22(ADLIGHT)+1 种基金European Regional Development Fund(80%)and Andalusian CTEICU/JA in the framework of the Operative Programme FEDER-Andalucia 2014-2020 through projects P20_01258(objective 01)and UPO-1381028(objective 1.2.3.)also contributed to the present researchWe also thank the laboratory of materials characterization INMALAB of Universidad Pablo de Olavide for experiments and technical support.
文摘The synthesis,characterisation and capability to selectively detect vapours of volatile organic compounds(VOCs)and nitroaromatic explosives of a new family of 2-dimensional rare earth(RE)MOFs based on a hexanuclear(RE^(3+))6 secondary building unit(SBU)is reported.The reaction of RE(NO_(3))_(3)with 4,4’-sulfonyldibenzoic acid(H_(2)SDBA)in the presence of 2-fluorobenzoic acid(HFBA)in DMF/MeOH at 100℃afforded compound[RE6(μ_(3)-OH/F)_(8)(SDBA)4(NO_(3))2(H_(2)O)_(6)]_(n)(UCY-15(RE);RE:Y,Eu,Gd,Tb,Dy,Ho,Er).
基金Supported by the Natural Science Foundation of Yan’an University (YDY2017-08)Innovation and Entrepreneurship Training Program of College Students of China (S202010719031)+1 种基金the Natural Science Foundation of Yulin (CXY-2020-065)the National Natural Science Foundation of China (21763028)。
文摘One hexanuclear cobalt cluster [Co_(2) ^(Ⅲ)Co_(4) ^(Ⅱ)(L)_(4)(CH_(3) COO)_(2)(MeO)_(4)]·MeOH(1) was synthesized by the reaction of H_(2)L(H_(2)L=2-((2-hydroxy-4-methoxy-benzylideneamino)methyl)phenol) and Co(OAc)2·4 H2O in MeOH under solvothermal conditions. Complex 1 crystalizes in the triclinic space group P1 with a = 14.397(3), b = 16.625(3), c = 18.992(4) A, α = 109.47(3)°, β = 99.24(3)°, γ = 112.37(3)°, Dc = 1.464 g/cm^(3), Z = 2, V = 3741.7(2) A^(3), the final R = 0.0781 and w R = 0.1436 for 13051 observed reflections with I > 2σ(I). In the structure of 1, two cobalt ions are in 3+ oxidation states and four cobalt ions are in 2+ valence states. The six cobalt atoms are held together by six phenolate oxygen atoms from four L^(2–) ligands, four oxygen atoms from two chelating acetates and four μ3-O atoms from four Me O– groups. The six cobalt atoms are located at six corners of four defective cubanes. Thus, complex 1 displays tetracubane-like topology. Solid-state dc magnetic susceptibilities were measured for 1 in the 2.0~300 K range. Antiferromagnetic interactions were determined for 1.
基金supported by the National Natural Science Foundation of China(nos.21671095 and 21901108)and startup funds from SUSTech.
文摘Postsynthesis of the paramagnetic square-shaped complex{[(Tp*Me)Fe(μ-CN)_(2)(CN)][Co(dmbpy)_(2)]}_(2)(BPh_(4))_(2)·6MeCN·H2O[1,Tp*Me=tris(3,4,5-trimethylpyrazole)-borate;dmbpy=4,4′-dimethyl-2,2′-bipyridine)]by grafting transition metal(II)thiocyanates via its terminal cyano groups afforded three hexanuclear[Fe_(2)Co_(2)M_(2)]clusters(M=Zn,2;Co,3;Cd,4).The peripheral metal-complex units serving as excellent electron acceptors were found to help stabilize the low-temperature state of Fe^(II,LS)–Co^(III,LS) within the complex core.
文摘A hexanuclear copper（Ⅰ） cluster [Cu6(C5H4NS)6] was synthesized by means of the hydrothermal reaction of [Cu(PPh3)2（MeCN）2]ClO4 with（2-mercaptopyridine-1-oxide） in the presence of 2-butanol,Et3N and water and characterized by elemental analysis,IR,TGA and solid state fluorescence spectroscopy as well as X-ray diffractometry.The crystallographic data for the title complex,C15H12Cu3N3S3,are Mr=521.08,monoclinic space group P2（1）/n and the cell parameters are: a=0.958 59（6） nm,b=（1.604 85（12） nm）,（c=）0.122 712（10） nm,β=108.863（2）°,V=1.786 4（2） nm3,Z=4,Dc=（1.937 Mg/m3）,R1=0.030 1,ωR2=0.031 5（I>2σ（I））,F（000）=1 032,μ=3.890 mm-1,R（int）=0.050 1,S=0.598.The title complex exhibits highly thermal stability and strong low energy fluorescence（（λ=）744 nm） when it is irradiated by the light（λ=468 nm） in solid state at room temperature.
基金financial support from the National Natural Science Foundation of China (NSFC, Nos. 21971040, 21971039 and 21773029)。
文摘The integration of lanthanide(Ln)ions and polyoxoniobates(PONbs)is challenging,and the know Ln-substituted PONbs are still scarce.This work introduces high-nuclear iso-Ln-oxo clusters into th PONb system.The first series of high-nuclear Ln-oxo clusters encapsulated heterometallic polyoxonio bates H_9[Na(H_(2)O)_(4)][Cu(en)_(2)]_(10){Ln_6(μ_(3)-OH)_6(Si Nb_(18)O_(54))_(3)}·18H_(2)O(1-Ln,en=ethylenediamine,Ln=Dy,Gd Tb,Ho,Er,Tm,Yb,Lu)based on flower-like{Ln_(6)(μ_(3)-OH)_(6)(Si Nb_(18)O_(54))_(3)}({Ln_6Si_(3)Nb_(54)})clusters hav been successfully synthesized via one-pot hydrothermal synthesis strategy.The flower-like polyoxoanio{Ln_6Si_(3)Nb_(54)}is consisted of three heteropolyoxoniobate{Si Nb_(18)O_(54)}clusters and one unique planar equ lateral triangle-shaped{Ln_6(μ_(3)-OH)_6}cluster,which presents the highest nuclear iso-Ln-oxo cluster i PONb chemistry.In{Ln_6(μ_(3)-OH)_6}cluster,each pair ofμ_(3)-OH groups link three Dy^(3+)ions to form a sma approximate equilateral triangle-shaped{Dy_(3)(OH)_(2)}cluster.Furthermore,the three{Dy_(3)(OH)_(2)}cluster comprise a bigger approximate equilateral triangle-shaped{Dy_6(μ_(3)-OH)_6}cluster.The reported hexanu clear{Ln_6}cluster skeletons are mostly octahedral,however,such equilateral triangle-shaped skeleton o the hexanuclear Ln-oxo cluster is first observed.The 1-Dy exhibits good water vapor adsorption capacit and ferromagnetic properties.
