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
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
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 energy-localized CNDO/2 molecular orbitals have been calculated for the cluster anions of [Co_6 (CO)_(14)] ̄(4-) and [Ni_2Co_4 (CO)_(14)] ̄(2-)in order to get a deeper insight into the nature of their skeletal bon...The energy-localized CNDO/2 molecular orbitals have been calculated for the cluster anions of [Co_6 (CO)_(14)] ̄(4-) and [Ni_2Co_4 (CO)_(14)] ̄(2-)in order to get a deeper insight into the nature of their skeletal bonding. The bonding characteristics of these hexanuclear carbonyl cobaltates are described from a localization bonding viewpoint. There are two typical M-CO bondings, one of which is formed by electron donation from the terminal and capping carbonyl ligands into the vacant hybrid orbitals on the metal atoms , leading to formation ofσ(C_t→Co) and σ(C_b→{Co_3})bonds. The other typical M-CO bonding is back donation of the lone d-electron pairs on the metal atoms into the carbonyl ligands, forming π(Co→C_t) bonds, σ(Co→{C_(b2)}) bonds and π(Co→{C_(b4)} ) bonds. It is found that there are no direct metalmetal bondings in the skeletons of these two cluster anions.The delocalization situation of the skeletal bonding electrons is briefly discussed.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.
文摘The energy-localized CNDO/2 molecular orbitals have been calculated for the cluster anions of [Co_6 (CO)_(14)] ̄(4-) and [Ni_2Co_4 (CO)_(14)] ̄(2-)in order to get a deeper insight into the nature of their skeletal bonding. The bonding characteristics of these hexanuclear carbonyl cobaltates are described from a localization bonding viewpoint. There are two typical M-CO bondings, one of which is formed by electron donation from the terminal and capping carbonyl ligands into the vacant hybrid orbitals on the metal atoms , leading to formation ofσ(C_t→Co) and σ(C_b→{Co_3})bonds. The other typical M-CO bonding is back donation of the lone d-electron pairs on the metal atoms into the carbonyl ligands, forming π(Co→C_t) bonds, σ(Co→{C_(b2)}) bonds and π(Co→{C_(b4)} ) bonds. It is found that there are no direct metalmetal bondings in the skeletons of these two cluster anions.The delocalization situation of the skeletal bonding electrons is briefly discussed.