Electron paramagnetic resonance(EPR)measurement of CsNiCl_(3)compound has been performed at 192 GHz in the temperature range from 300 to 5 K,along the axes of main g tensor.The energy levels and the g-factors are calc...Electron paramagnetic resonance(EPR)measurement of CsNiCl_(3)compound has been performed at 192 GHz in the temperature range from 300 to 5 K,along the axes of main g tensor.The energy levels and the g-factors are calculated.The linear thermalexpansion coefficient(2.77×10^(-5)K^(-1))for the Ni^(2+)-Cl^(-)bond distance is studied by combining EPR and optical absorption spectra with changing temperature.展开更多
A new compound 1-[trans-4-((N-ethylcarbazolyl) vinyl) phenyl]imidazole(C25H22N3,Mr=364.46)has been synthesized,and its crystal structure was determined by single-crystal X-ray diffraction method.The crystal is of mono...A new compound 1-[trans-4-((N-ethylcarbazolyl) vinyl) phenyl]imidazole(C25H22N3,Mr=364.46)has been synthesized,and its crystal structure was determined by single-crystal X-ray diffraction method.The crystal is of monoclinic,space group P21/c with a=9.298(2) A,b=8.648(2) A,c=25.394(7) A,β=110.46(3)°,V=1912.9(8) A3,Z=4,Dc=1.266g/cm3,μ=0.075mm-1,F(000)=772,The structure was refined to R=0.0685 and wR=0.1612 for 3570 unique reflections with Rint=0.0645.The structural determination shows that the molecular structure is a perfectly planar π-conjugated system,and there is a high electronic delocalization in the molecule.The compound shows photoluminescence with a maximum emission at 439nm and a shoulder emission at 458nm upon the maximum-excitation wavelength at 264nm.展开更多
The calculation of the complex matrixes in odd triangular symmetry was accomplished.The configurations of the coordination unit with various triangular symmetries and different ligand numbers were discussed.On the bas...The calculation of the complex matrixes in odd triangular symmetry was accomplished.The configurations of the coordination unit with various triangular symmetries and different ligand numbers were discussed.On the basis of the double-sphere coordination point-charge (DSCPCF) model,the detailed forms of the DSCPCF parameters Bmk and the expressions of the perturbation matrix elements in triangular field (D3,D3h,D3d) were derived.Thereby,the calculation scheme of coordination field perturbation energy of the rare earth complexes with triangular symmetry was constructed After the calculation scheme was programmed,the Stark energies of the crystalline TbAl3(BO3)4 were calculated The results were considerably close to the experimental values展开更多
The studies of Mössbauer spectroscopy and magnetic properties for complex Fe(tpa)(NCS)_(2) exhibit that low spin→high spin(HS)transition may be thermally induced.The impurities such as HS-Fe^(2+) residue and HS-...The studies of Mössbauer spectroscopy and magnetic properties for complex Fe(tpa)(NCS)_(2) exhibit that low spin→high spin(HS)transition may be thermally induced.The impurities such as HS-Fe^(2+) residue and HS-Fe^(3+),that were caused by compound preparation,play a significant role in the investigation of spin transition curve.The Mössbauer spectroscopy is used to observe the impurities as separated forms from the spin transition phase directly,and the magnetic susceptibility measurement is used to determine the total paramagnetism from all HS phases.With these two useful tools,an exact spin transition curve was defined by removing the magnetic contribution of the impurities.展开更多
I.THEORY The Hamiltonian of rare earth ions can be written as where （?）<sub>Coul</sub> is the Coulomb interaction, （?）<sub>s·o</sub>, the spin-orbit interaction, （?）<sub>Ca<...I.THEORY The Hamiltonian of rare earth ions can be written as where （?）<sub>Coul</sub> is the Coulomb interaction, （?）<sub>s·o</sub>, the spin-orbit interaction, （?）<sub>Ca</sub>, Casimir operator interaction in the interaction of different configurations in Coulomb interaction, and （?）<sub>cf</sub> is ligand field interaction. A method to treat the rare earth ions is to diagonalize （?）<sub>Coul</sub>, （?）<sub>s.o</sub> and （?）<sub>Ca</sub>, in （1） simultaneously and then to determine the eigenfunction of "展开更多
Two series of Schiff base alkylcobalt complexes: alkylcobaltbis （salicylaldehyde） ethylendiimine RCo （Salen） L and a kind of new Coenzyme B<sub>12</sub> model compounds alkylcobaltbis （salicylaldehyde...Two series of Schiff base alkylcobalt complexes: alkylcobaltbis （salicylaldehyde） ethylendiimine RCo （Salen） L and a kind of new Coenzyme B<sub>12</sub> model compounds alkylcobaltbis （salicylaldehyde）-2, 3-dimethyl-2, 3 butadiamine RCo （SB） L were展开更多
Since Pederson discovered crown ethers, many complexes containing crown and metal ions have been synthesized. The metal ions in the complexes mainly ethers are alkali and alkaliearth metal ions. Some transition metal ...Since Pederson discovered crown ethers, many complexes containing crown and metal ions have been synthesized. The metal ions in the complexes mainly ethers are alkali and alkaliearth metal ions. Some transition metal complexes have been reported but not in large numbers. In order to reveal the structure character of this kind of compound we determined the crystal structure of （VOCl2.4H2O）（18-crown-6） by X-ray diffraction method to investigate the way of linking crown ether with vanadium.展开更多
Ⅰ. INTRODUCTION A few platinum complexes having antitumor properties have attracted much interest in recent years, Now we have synthesized and tested the Pt(Ⅳ) malonato complex, which appears to exhibit significant ...Ⅰ. INTRODUCTION A few platinum complexes having antitumor properties have attracted much interest in recent years, Now we have synthesized and tested the Pt(Ⅳ) malonato complex, which appears to exhibit significant activity on W-256 cancer. For this reason and in order to obtain more interesting information on the Pt(Ⅳ) malonato complex, we have determined the crystal and molecular structure. In the present paper we are reporting this result.展开更多
The crystal structure of the title complex was measured, in which the two zinc atoms with coordination polyhedron of distorted tetragonal pyramid (TP) are bridged by an imidazolate in the apical position of the TP for...The crystal structure of the title complex was measured, in which the two zinc atoms with coordination polyhedron of distorted tetragonal pyramid (TP) are bridged by an imidazolate in the apical position of the TP forming a dimer. The isomorphous [(trien)Cu(im)Zn(trien)](ClO4)3·H2O complex was doped in the title complex and the recorded single-crystal ESR spectra by fitting gave two sets of the principal values of g and A tensors, which were assigned to the physically distinct sites of the two magnetically equivalent molecules in the unit cell. Lattice distortion at the Cu(II) ion sites and the bonding parameters of Cu(II) ions are further calculated, and the bonding nature of Cu(II) ions is discussed.展开更多
The number of reports on the transition metal complex （Mn2Cl2·8H2O）（18-crown-6）Cl2 has been small. In our determination of the crystal structure of （VOCl2·4H2O）（18-crown-6）, we discovered that there ...The number of reports on the transition metal complex （Mn2Cl2·8H2O）（18-crown-6）Cl2 has been small. In our determination of the crystal structure of （VOCl2·4H2O）（18-crown-6）, we discovered that there are some characters in the linking crown ether with transition metal ions. In order to reveal the structure characters of this kind of compounds, we have determined the crystal structure of （Mn2Cl2·8H2O） （18-crown-6）Cl2 by X-ray diffraction method and discussed the way of linking crown ether with transition metal ions.展开更多
Recently much effort has been made to study the thermolytic reactivity oforganolanthanide complexes. These studies have mainly involved disproportionation,β-hydrogen elimination, and other reactions but the C-H activ...Recently much effort has been made to study the thermolytic reactivity oforganolanthanide complexes. These studies have mainly involved disproportionation,β-hydrogen elimination, and other reactions but the C-H activation on the Cp展开更多
The basic approximation of the MNDO method is applied to the SCF-MO theory of nu- clear magnetic shielding constants.Gauge-invariant atomic orbitais(GIAO)and derived equations are used to cal- culate NMR chemical shif...The basic approximation of the MNDO method is applied to the SCF-MO theory of nu- clear magnetic shielding constants.Gauge-invariant atomic orbitais(GIAO)and derived equations are used to cal- culate NMR chemical shifts.A more simple and effective calculation of integration for operators 1/r_M,L_M and L_M/r_M described in our previous paper is used.By proper selection of MNDO parameters together with the two-center approximation,a satisfactory agreement between computational and experimental ^(13)C and ^(19)F chemi- cal shifts is obtained for a representative set of fluorides.展开更多
Hydrolysis of DNA is an important enzymatic reaction , but it is exceedingly difficult to mimic in the laboratory because of the stability of hydrolysis of DNA. In this paper, the cleavage activity of complexes formed...Hydrolysis of DNA is an important enzymatic reaction , but it is exceedingly difficult to mimic in the laboratory because of the stability of hydrolysis of DNA. In this paper, the cleavage activity of complexes formed between Cu(Ⅱ) and four different amino acid or amino acid methyl ester on DNA is studied by gel elec-trophoresis. It is found that DNA could be cleaved by Cu(Ⅱ)-L-His and Cu(Ⅱ)-L-His methyl ester complexes and the efficiency of cleavage is largely dependent on the metal ion-to-ligand ratio. Further experiments show that the cleavage of DNA mediated by Cu(Ⅱ)-L-His complexes occurs via a hydrolytic mechanism and the active chemical species that affects DNA cleavage is proposed to be MI2H+ and ML2H22+.展开更多
Davidson and Clark’s equations for calculating the local spin of molecules were rewritten and simplified as matrices algebra. By applying our program, we calculated the local spin of O2 and NO molecules and obtained ...Davidson and Clark’s equations for calculating the local spin of molecules were rewritten and simplified as matrices algebra. By applying our program, we calculated the local spin of O2 and NO molecules and obtained almost the same results as those by Davidson and Clark’s method. The local spin and the magnetic coupling constant J of the simple Van der Waals complex HHeH were calculated as well to investigate the relationship between the geometric structures and magnetic values.展开更多
基金Supported by the State Key Project of the Fundamental Research,and the National Natural Science Foundation of China.
文摘Electron paramagnetic resonance(EPR)measurement of CsNiCl_(3)compound has been performed at 192 GHz in the temperature range from 300 to 5 K,along the axes of main g tensor.The energy levels and the g-factors are calculated.The linear thermalexpansion coefficient(2.77×10^(-5)K^(-1))for the Ni^(2+)-Cl^(-)bond distance is studied by combining EPR and optical absorption spectra with changing temperature.
基金supported by a grants for the Education Committee of Anhui Province(KJ2010B126)
文摘A new compound 1-[trans-4-((N-ethylcarbazolyl) vinyl) phenyl]imidazole(C25H22N3,Mr=364.46)has been synthesized,and its crystal structure was determined by single-crystal X-ray diffraction method.The crystal is of monoclinic,space group P21/c with a=9.298(2) A,b=8.648(2) A,c=25.394(7) A,β=110.46(3)°,V=1912.9(8) A3,Z=4,Dc=1.266g/cm3,μ=0.075mm-1,F(000)=772,The structure was refined to R=0.0685 and wR=0.1612 for 3570 unique reflections with Rint=0.0645.The structural determination shows that the molecular structure is a perfectly planar π-conjugated system,and there is a high electronic delocalization in the molecule.The compound shows photoluminescence with a maximum emission at 439nm and a shoulder emission at 458nm upon the maximum-excitation wavelength at 264nm.
基金Project supported by the National Natural Science Foundation of China
文摘The calculation of the complex matrixes in odd triangular symmetry was accomplished.The configurations of the coordination unit with various triangular symmetries and different ligand numbers were discussed.On the basis of the double-sphere coordination point-charge (DSCPCF) model,the detailed forms of the DSCPCF parameters Bmk and the expressions of the perturbation matrix elements in triangular field (D3,D3h,D3d) were derived.Thereby,the calculation scheme of coordination field perturbation energy of the rare earth complexes with triangular symmetry was constructed After the calculation scheme was programmed,the Stark energies of the crystalline TbAl3(BO3)4 were calculated The results were considerably close to the experimental values
基金Supported by the Funds of Chinese Postdoctoralthe National Natural Science Foundation of China.
文摘The studies of Mössbauer spectroscopy and magnetic properties for complex Fe(tpa)(NCS)_(2) exhibit that low spin→high spin(HS)transition may be thermally induced.The impurities such as HS-Fe^(2+) residue and HS-Fe^(3+),that were caused by compound preparation,play a significant role in the investigation of spin transition curve.The Mössbauer spectroscopy is used to observe the impurities as separated forms from the spin transition phase directly,and the magnetic susceptibility measurement is used to determine the total paramagnetism from all HS phases.With these two useful tools,an exact spin transition curve was defined by removing the magnetic contribution of the impurities.
文摘I.THEORY The Hamiltonian of rare earth ions can be written as where （?）<sub>Coul</sub> is the Coulomb interaction, （?）<sub>s·o</sub>, the spin-orbit interaction, （?）<sub>Ca</sub>, Casimir operator interaction in the interaction of different configurations in Coulomb interaction, and （?）<sub>cf</sub> is ligand field interaction. A method to treat the rare earth ions is to diagonalize （?）<sub>Coul</sub>, （?）<sub>s.o</sub> and （?）<sub>Ca</sub>, in （1） simultaneously and then to determine the eigenfunction of "
文摘Two series of Schiff base alkylcobalt complexes: alkylcobaltbis （salicylaldehyde） ethylendiimine RCo （Salen） L and a kind of new Coenzyme B<sub>12</sub> model compounds alkylcobaltbis （salicylaldehyde）-2, 3-dimethyl-2, 3 butadiamine RCo （SB） L were
文摘Since Pederson discovered crown ethers, many complexes containing crown and metal ions have been synthesized. The metal ions in the complexes mainly ethers are alkali and alkaliearth metal ions. Some transition metal complexes have been reported but not in large numbers. In order to reveal the structure character of this kind of compound we determined the crystal structure of （VOCl2.4H2O）（18-crown-6） by X-ray diffraction method to investigate the way of linking crown ether with vanadium.
文摘Ⅰ. INTRODUCTION A few platinum complexes having antitumor properties have attracted much interest in recent years, Now we have synthesized and tested the Pt(Ⅳ) malonato complex, which appears to exhibit significant activity on W-256 cancer. For this reason and in order to obtain more interesting information on the Pt(Ⅳ) malonato complex, we have determined the crystal and molecular structure. In the present paper we are reporting this result.
文摘The crystal structure of the title complex was measured, in which the two zinc atoms with coordination polyhedron of distorted tetragonal pyramid (TP) are bridged by an imidazolate in the apical position of the TP forming a dimer. The isomorphous [(trien)Cu(im)Zn(trien)](ClO4)3·H2O complex was doped in the title complex and the recorded single-crystal ESR spectra by fitting gave two sets of the principal values of g and A tensors, which were assigned to the physically distinct sites of the two magnetically equivalent molecules in the unit cell. Lattice distortion at the Cu(II) ion sites and the bonding parameters of Cu(II) ions are further calculated, and the bonding nature of Cu(II) ions is discussed.
文摘The number of reports on the transition metal complex （Mn2Cl2·8H2O）（18-crown-6）Cl2 has been small. In our determination of the crystal structure of （VOCl2·4H2O）（18-crown-6）, we discovered that there are some characters in the linking crown ether with transition metal ions. In order to reveal the structure characters of this kind of compounds, we have determined the crystal structure of （Mn2Cl2·8H2O） （18-crown-6）Cl2 by X-ray diffraction method and discussed the way of linking crown ether with transition metal ions.
基金Project supported by the National Committee of Science and Technology.
文摘Recently much effort has been made to study the thermolytic reactivity oforganolanthanide complexes. These studies have mainly involved disproportionation,β-hydrogen elimination, and other reactions but the C-H activation on the Cp
文摘The basic approximation of the MNDO method is applied to the SCF-MO theory of nu- clear magnetic shielding constants.Gauge-invariant atomic orbitais(GIAO)and derived equations are used to cal- culate NMR chemical shifts.A more simple and effective calculation of integration for operators 1/r_M,L_M and L_M/r_M described in our previous paper is used.By proper selection of MNDO parameters together with the two-center approximation,a satisfactory agreement between computational and experimental ^(13)C and ^(19)F chemi- cal shifts is obtained for a representative set of fluorides.
基金Project supported by the National Natural Science Foundation of China (No. 29771023)the Natural Science Foundation of Shanxi Province
文摘Hydrolysis of DNA is an important enzymatic reaction , but it is exceedingly difficult to mimic in the laboratory because of the stability of hydrolysis of DNA. In this paper, the cleavage activity of complexes formed between Cu(Ⅱ) and four different amino acid or amino acid methyl ester on DNA is studied by gel elec-trophoresis. It is found that DNA could be cleaved by Cu(Ⅱ)-L-His and Cu(Ⅱ)-L-His methyl ester complexes and the efficiency of cleavage is largely dependent on the metal ion-to-ligand ratio. Further experiments show that the cleavage of DNA mediated by Cu(Ⅱ)-L-His complexes occurs via a hydrolytic mechanism and the active chemical species that affects DNA cleavage is proposed to be MI2H+ and ML2H22+.
基金Major State Bas ic Research Development Program of Sic.and Tech.Mhinistry(Gant No.G 200077500)Major Project of Resesrch of NSFC(Grcnt No.90101028).
文摘Davidson and Clark’s equations for calculating the local spin of molecules were rewritten and simplified as matrices algebra. By applying our program, we calculated the local spin of O2 and NO molecules and obtained almost the same results as those by Davidson and Clark’s method. The local spin and the magnetic coupling constant J of the simple Van der Waals complex HHeH were calculated as well to investigate the relationship between the geometric structures and magnetic values.
