The possible geometries of Fe(HCN)n (n = 1~6) compounds were studied by using + DFT/UB3LYP/6-31G(2df) method. The structure and ground state ...The possible geometries of Fe(HCN)n (n = 1~6) compounds were studied by using + DFT/UB3LYP/6-31G(2df) method. The structure and ground state of each fragmental ion are C∞v (4Σ+ or Σ ), D∞h (4Σg ), D3 (4A1 ), C2 or Td or C3v (4A1), and D3 (4A1 ) or C4 ( A1 ) sequentially 6 + + ′ ′ ′ 2 ′ h v h v with n = 1～5. For the compound Fe(HCN)6 , the possible geometry was not obtained. The + sequential incremental interaction energy (–?(?E)), dissociation energy (?D0), enthalpy (–?(?H)) and Gibbs free energy (–?(?G)), and frequencies for HCN-Fe(HCN)n + -1 were also calculated, and the results are all in good agreement with the experiments. The bond length of Fe–N is lengthened with the increase of cluster size, and the strength of Fe+–N coordination bond varies nonmon- tonically as increasing the number of ligands. The Fe+–N bond of Fe(HCN)2 is the strongest in all + compounds.展开更多
A three-dimensional（3D） coordination polymer,[Cd（SC）（DPPD）]_n（1,H_2SC = succinic acid and DPPD = 3,6-di（4-pyridyl）pyridazine）,has been synthesized by the solvothermal reaction of Cd（NO_3）_2·4H_2O with...A three-dimensional（3D） coordination polymer,[Cd（SC）（DPPD）]_n（1,H_2SC = succinic acid and DPPD = 3,6-di（4-pyridyl）pyridazine）,has been synthesized by the solvothermal reaction of Cd（NO_3）_2·4H_2O with H_2 SC and DPPD at 120 ℃ in DMF solvent. Compound 1 crystallizes in the monoclinic system,space group P2_1/c,with a = 10.7993（4）,b = 11.7705（3）,c = 13.5336（6） A,V = 1678.89（11） A^3,Z = 4,C18H14N4O_4 Cd,M_r = 462.73,D_c = 1.831 g/cm^3,μ = 1.335 mm^（-1）,F（000） = 920.0,the final R = 0.0500 and wR = 0.1567 for 3714 observed reflections with I 〉 2s（I）. In compound 1,the Cd（Ⅱ） ions are linked by the SC^2– ligands to give a two-dimensional（2D） undulating sheet based on the centrosymmetric dinuclear Cd_2（COO）_2 units. The 2D sheets are further connected by the DPPD ligands to produce a 3D structure,which is a 6-connected（4^4·6·^10·8） topological network based on the dinuclear Cd_2（COO）_2 node. Compound 1 exhibits a photoluminescent emission with a maximum at 540 nm upon excitation at 460 nm.展开更多
The magnetic properties and the magnetic entropy change AS have been investigated for Gd6Co1.67Si3 compounds with a second-order phase transition. The saturation moment at 5 K and the Curie temperature TC are 38.1μB ...The magnetic properties and the magnetic entropy change AS have been investigated for Gd6Co1.67Si3 compounds with a second-order phase transition. The saturation moment at 5 K and the Curie temperature TC are 38.1μB and 298 K, respectively. The AS originates from a reversible second-order magnetic transition around TC and its value reaches 5.2 J/kg.K for a magnetic field change from 0 to 5T. The refrigerant capacity （RC） of Gd6Co1.67Si3 are calculated by using the methods given in Refs.[12] and [21], respectively, for a field change of 0 5T and its values are 310 and 440 J/kg, which is larger than those of some magnetocaloric materials with a first-order phase transition.展开更多
A new compound Sr6Sn2Nb8O30 was found in the ternary system of SrO-SnO2-Nb2O5. The transparent colorless crystal with needle-like shape can be grown by flux method. The crystal structure of new compound was determined...A new compound Sr6Sn2Nb8O30 was found in the ternary system of SrO-SnO2-Nb2O5. The transparent colorless crystal with needle-like shape can be grown by flux method. The crystal structure of new compound was determined by X-ray diffraction, and its belongs to tungsten bronze structure. Sr6Sn2Nb8O30 crystallizes in orthorhombic system with unit cell parameters a= 17. 579 (DA,6= 17. 509(DA,c=7. 7880(5)A,Z = 4 and space group Cmm2.展开更多
Magnetic entropy change （△SM） and refrigerant capacity （RC） of Ce6Ni2Si3-type Gd6Co1.67Si2.5Geo.5 compounds have been investigated. The Gd6Col.67Si2.5Geo.5 undergoes a reversible second-order phase transition at ...Magnetic entropy change （△SM） and refrigerant capacity （RC） of Ce6Ni2Si3-type Gd6Co1.67Si2.5Geo.5 compounds have been investigated. The Gd6Col.67Si2.5Geo.5 undergoes a reversible second-order phase transition at the Curie temperature Tc = 296 K. The high saturation magnetization leads to a large ASM and the maximal value of △SM is found to be 5.9 J/kg. K around TC for a field change of 0-5 T. A broad distribution of the △SM peak is observed and the full width at half maximum of the △SM peak is about 101 K under a magnetic field of 5 T. The large RC is found around TC and its value is 424 J/kg.展开更多
The [Zr6(μ2-Cl)12Cl6H4]3- ion with C4v Symmetry in the title compounds has been calculated by DV-Xα program. The calculated results show that ther is almost no available covalence bonding between zirconium ato...The [Zr6(μ2-Cl)12Cl6H4]3- ion with C4v Symmetry in the title compounds has been calculated by DV-Xα program. The calculated results show that ther is almost no available covalence bonding between zirconium atoms and significant Zr 4d AO compositions in the MOs. but there are much stronger Zr-Cl(bridging) bonding. All analysis results suggest that these compounds would be the cluster with Zr6Cl12 cage linked by Zr-Cl bridging bonding plus six Cl teminal ligands rather than the hexazirconium cluster in view of the chemical bonding.展开更多
Magnetic properties and magnetocaloric effects of Tb6Coi.67Si3 have been investigated by magnetization measurement. This compound is of a hexagonal Ce6Ni2Si3-type structure with a saturation magnetization of 187emu/g ...Magnetic properties and magnetocaloric effects of Tb6Coi.67Si3 have been investigated by magnetization measurement. This compound is of a hexagonal Ce6Ni2Si3-type structure with a saturation magnetization of 187emu/g at 5 K and a reversible second-order magnetic transition at Curie temperature TC = 186K. A magnetic entropy change △S = 7J·kg^-1·K^-1 is observed for a magnetic field change from 0 to 5T. A large value of refrigerant capacity （RC） is found to be 330 J/kg for fields ranging from 0 to ST. The large RC, the reversible magnetization around Tc and the easy fabrication make the Tb6Co1.67Si3 compound a suitable candidate for magnetic refrigerants in a corresponding temperature range.展开更多
Compound Co_3(o-HOC_6H_4S)_2(o-OC_6H_4S)_2(PEt_3)_3 was obtained by reaction of CoCl_2, o-HOC_6H_4SH(H_2mD)and PEt_3 in ethanol in the presence of NaOCH_3.The three Co atoms are triangularly arranged and asymmetricall...Compound Co_3(o-HOC_6H_4S)_2(o-OC_6H_4S)_2(PEt_3)_3 was obtained by reaction of CoCl_2, o-HOC_6H_4SH(H_2mD)and PEt_3 in ethanol in the presence of NaOCH_3.The three Co atoms are triangularly arranged and asymmetrically bridged by four S and one O atoms from the four H_2mp ligands and terminally ligated by one O and three P atoms.Two free hydroxyl groups form two internal hydrogen bonds with adjacent oxo donor atoms.展开更多
The space group of PrCo_(12)B_6,compound has been determined using the convergent beam elec- tron diffraction method.The space group is found to be R3m.
The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethan...The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in the presence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c, Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4; Dc=1.78g/cm^3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]cluster core and t-(dtp)^(-1)ligands are retained and only μ-bridged(dtp)^(-1)ligands are substituted by(C_6H_5CO_2)^(-1)in the substitution reaction,thus producing the new title cluster compound,the structure of which contains two species of bidentate ligand.展开更多
Objective:Glucose-6-phosphate isomerase(GPI)deficiency is a rare hereditary nonspherocytic hemolytic anemia caused by GPI gene variants.This disorder exhibits wide heterogeneity in its clinical manifestations and mole...Objective:Glucose-6-phosphate isomerase(GPI)deficiency is a rare hereditary nonspherocytic hemolytic anemia caused by GPI gene variants.This disorder exhibits wide heterogeneity in its clinical manifestations and molecular characteristics,often posing challenges for precise diagnoses using conventional methods.To this end,this study aimed to identify the novel variants responsible for GPI deficiency in a Chinese family.Methods:The clinical manifestations of the patient were summarized and analyzed for GPI deficiency phenotype diagnosis.Novel compound heterozygous variants of the GPI gene,c.174C>A(p.Asn58Lys)and c.1538G>T(p.Trp513Leu),were identified using whole-exome and Sanger sequencing.The AlphaFold program and Chimera software were used to analyze the effects of compound heterozygous variants on GPI structure.Results:By characterizing 53 GPI missense/nonsense variants from previous literature and two novel missense variants identified in this study,we found that most variants were located in exons 3,4,12,and 18,with a few localized in exons 8,9,and 14.This study identified novel compound heterozygous variants associated with GPI deficiency.These pathogenic variants disrupt hydrogen bonds formed by highly conserved GPI amino acids.Conclusion:Early family-based sequencing analyses,especially for patients with congenital anemia,can help increase diagnostic accuracy for GPI deficiency,improve child healthcare,and enable genetic counseling.展开更多
基金This research was supported by the National Natural Science Foundation of China (20273013 20303002)+1 种基金 the Key Foundation of Fujian Province (K02012) the Foundation of State Key Laboratory of Structural Chemistry (020051) and of Fuzhou University
文摘The possible geometries of Fe(HCN)n (n = 1~6) compounds were studied by using + DFT/UB3LYP/6-31G(2df) method. The structure and ground state of each fragmental ion are C∞v (4Σ+ or Σ ), D∞h (4Σg ), D3 (4A1 ), C2 or Td or C3v (4A1), and D3 (4A1 ) or C4 ( A1 ) sequentially 6 + + ′ ′ ′ 2 ′ h v h v with n = 1～5. For the compound Fe(HCN)6 , the possible geometry was not obtained. The + sequential incremental interaction energy (–?(?E)), dissociation energy (?D0), enthalpy (–?(?H)) and Gibbs free energy (–?(?G)), and frequencies for HCN-Fe(HCN)n + -1 were also calculated, and the results are all in good agreement with the experiments. The bond length of Fe–N is lengthened with the increase of cluster size, and the strength of Fe+–N coordination bond varies nonmon- tonically as increasing the number of ligands. The Fe+–N bond of Fe(HCN)2 is the strongest in all + compounds.
基金Supported by the National Natural Science Foundation of China(No.21361011 and 21101081)Science Founds of State key Laboratory of Structural Chemistry(20130011)
文摘A three-dimensional（3D） coordination polymer,[Cd（SC）（DPPD）]_n（1,H_2SC = succinic acid and DPPD = 3,6-di（4-pyridyl）pyridazine）,has been synthesized by the solvothermal reaction of Cd（NO_3）_2·4H_2O with H_2 SC and DPPD at 120 ℃ in DMF solvent. Compound 1 crystallizes in the monoclinic system,space group P2_1/c,with a = 10.7993（4）,b = 11.7705（3）,c = 13.5336（6） A,V = 1678.89（11） A^3,Z = 4,C18H14N4O_4 Cd,M_r = 462.73,D_c = 1.831 g/cm^3,μ = 1.335 mm^（-1）,F（000） = 920.0,the final R = 0.0500 and wR = 0.1567 for 3714 observed reflections with I 〉 2s（I）. In compound 1,the Cd（Ⅱ） ions are linked by the SC^2– ligands to give a two-dimensional（2D） undulating sheet based on the centrosymmetric dinuclear Cd_2（COO）_2 units. The 2D sheets are further connected by the DPPD ligands to produce a 3D structure,which is a 6-connected（4^4·6·^10·8） topological network based on the dinuclear Cd_2（COO）_2 node. Compound 1 exhibits a photoluminescent emission with a maximum at 540 nm upon excitation at 460 nm.
基金Project supported by the National Natural Science Foundation of China (Grant Nos 50571112 and 50731007)the National Basic Research Program of China (Grant No 2006CB601101)the Basic Research Program of Chinese Academy of Sciences, China (Grant No KJCX2-YW-W02)
文摘The magnetic properties and the magnetic entropy change AS have been investigated for Gd6Co1.67Si3 compounds with a second-order phase transition. The saturation moment at 5 K and the Curie temperature TC are 38.1μB and 298 K, respectively. The AS originates from a reversible second-order magnetic transition around TC and its value reaches 5.2 J/kg.K for a magnetic field change from 0 to 5T. The refrigerant capacity （RC） of Gd6Co1.67Si3 are calculated by using the methods given in Refs.[12] and [21], respectively, for a field change of 0 5T and its values are 310 and 440 J/kg, which is larger than those of some magnetocaloric materials with a first-order phase transition.
基金Funded by International Centre for Diffraction Data(ICDD).
文摘A new compound Sr6Sn2Nb8O30 was found in the ternary system of SrO-SnO2-Nb2O5. The transparent colorless crystal with needle-like shape can be grown by flux method. The crystal structure of new compound was determined by X-ray diffraction, and its belongs to tungsten bronze structure. Sr6Sn2Nb8O30 crystallizes in orthorhombic system with unit cell parameters a= 17. 579 (DA,6= 17. 509(DA,c=7. 7880(5)A,Z = 4 and space group Cmm2.
基金Project supported by the National Natural Science Foundation of China （Grant Nos. 11004204 and 51001114）, the Knowledge Inno- vation Project of the Chinese Academy of Sciences, and the National Basic Research Program of China （Grant No. 2006CB601101）.
文摘Magnetic entropy change （△SM） and refrigerant capacity （RC） of Ce6Ni2Si3-type Gd6Co1.67Si2.5Geo.5 compounds have been investigated. The Gd6Col.67Si2.5Geo.5 undergoes a reversible second-order phase transition at the Curie temperature Tc = 296 K. The high saturation magnetization leads to a large ASM and the maximal value of △SM is found to be 5.9 J/kg. K around TC for a field change of 0-5 T. A broad distribution of the △SM peak is observed and the full width at half maximum of the △SM peak is about 101 K under a magnetic field of 5 T. The large RC is found around TC and its value is 424 J/kg.
文摘The [Zr6(μ2-Cl)12Cl6H4]3- ion with C4v Symmetry in the title compounds has been calculated by DV-Xα program. The calculated results show that ther is almost no available covalence bonding between zirconium atoms and significant Zr 4d AO compositions in the MOs. but there are much stronger Zr-Cl(bridging) bonding. All analysis results suggest that these compounds would be the cluster with Zr6Cl12 cage linked by Zr-Cl bridging bonding plus six Cl teminal ligands rather than the hexazirconium cluster in view of the chemical bonding.
基金Project supported by the National Natural Science Foundation of China （Grant Nos 50571112 and 50731007）, the National Basic Research Program of China （Grant No 2006CB601101） and the Basic Research Program of Chinese Academy of Sciences （Grant No KJCX2-YW-W02）.
文摘Magnetic properties and magnetocaloric effects of Tb6Coi.67Si3 have been investigated by magnetization measurement. This compound is of a hexagonal Ce6Ni2Si3-type structure with a saturation magnetization of 187emu/g at 5 K and a reversible second-order magnetic transition at Curie temperature TC = 186K. A magnetic entropy change △S = 7J·kg^-1·K^-1 is observed for a magnetic field change from 0 to 5T. A large value of refrigerant capacity （RC） is found to be 330 J/kg for fields ranging from 0 to ST. The large RC, the reversible magnetization around Tc and the easy fabrication make the Tb6Co1.67Si3 compound a suitable candidate for magnetic refrigerants in a corresponding temperature range.
文摘Compound Co_3(o-HOC_6H_4S)_2(o-OC_6H_4S)_2(PEt_3)_3 was obtained by reaction of CoCl_2, o-HOC_6H_4SH(H_2mD)and PEt_3 in ethanol in the presence of NaOCH_3.The three Co atoms are triangularly arranged and asymmetrically bridged by four S and one O atoms from the four H_2mp ligands and terminally ligated by one O and three P atoms.Two free hydroxyl groups form two internal hydrogen bonds with adjacent oxo donor atoms.
文摘The space group of PrCo_(12)B_6,compound has been determined using the convergent beam elec- tron diffraction method.The space group is found to be R3m.
文摘The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in the presence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c, Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4; Dc=1.78g/cm^3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]cluster core and t-(dtp)^(-1)ligands are retained and only μ-bridged(dtp)^(-1)ligands are substituted by(C_6H_5CO_2)^(-1)in the substitution reaction,thus producing the new title cluster compound,the structure of which contains two species of bidentate ligand.
文摘Objective:Glucose-6-phosphate isomerase(GPI)deficiency is a rare hereditary nonspherocytic hemolytic anemia caused by GPI gene variants.This disorder exhibits wide heterogeneity in its clinical manifestations and molecular characteristics,often posing challenges for precise diagnoses using conventional methods.To this end,this study aimed to identify the novel variants responsible for GPI deficiency in a Chinese family.Methods:The clinical manifestations of the patient were summarized and analyzed for GPI deficiency phenotype diagnosis.Novel compound heterozygous variants of the GPI gene,c.174C>A(p.Asn58Lys)and c.1538G>T(p.Trp513Leu),were identified using whole-exome and Sanger sequencing.The AlphaFold program and Chimera software were used to analyze the effects of compound heterozygous variants on GPI structure.Results:By characterizing 53 GPI missense/nonsense variants from previous literature and two novel missense variants identified in this study,we found that most variants were located in exons 3,4,12,and 18,with a few localized in exons 8,9,and 14.This study identified novel compound heterozygous variants associated with GPI deficiency.These pathogenic variants disrupt hydrogen bonds formed by highly conserved GPI amino acids.Conclusion:Early family-based sequencing analyses,especially for patients with congenital anemia,can help increase diagnostic accuracy for GPI deficiency,improve child healthcare,and enable genetic counseling.
