Two large-pore metal-doped aluminophosphates, Mn4Al5（PO4 ）12[N（ C2H4NH3）3]3 [ N（C2H4NH3）2·（C2H4NH2）]（NH4）2·14H=O（Mn4-NJU） and Co4Al5（PO4）12[N（C2H,NH3）3][N（C2H4NH3）2（C2H4NH2）]3· （ N...Two large-pore metal-doped aluminophosphates, Mn4Al5（PO4 ）12[N（ C2H4NH3）3]3 [ N（C2H4NH3）2·（C2H4NH2）]（NH4）2·14H=O（Mn4-NJU） and Co4Al5（PO4）12[N（C2H,NH3）3][N（C2H4NH3）2（C2H4NH2）]3· （ NH4 ）4· 13H2O （ Co4-NJU） , which have the same open framework structures, were hydrothermally synthesized. The structures of these compounds consist of TO4 tetrahedra, which are linked together by corner-sharing to form an open framework with unique intersecting twelve-membered ring channels in three dimensions. The compounds crystallize in cubic space group I（-4）3m with α= 1. 6795（2） nm and V=4. 7374（9） nm^3 for Mn4-NJU, and a=1. 67372（19） nm and V = 4. 6887 （9） nm^3 for Co4-NJU, respectively. Single crystal structure analyses show that the protruding O atoms of the frameworks of the compounds are linked to protonated 4-（ 2-aminoethyl ）diethylenetriamine （TREN, C6H18N4 ） ions in the windows by means of hydrogen-bonding under the hydrothermal condition. It is also found that the components inside the super cages of the compounds are changeable, and the metal ions M^2＋ （M = Mn, Co） and Al^3＋ disorderedly occupy the same crystallographic positions.展开更多
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
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
Crystal structure of the title compound, macrocyclic tetrabenzo(b ,f,J, n ) [ 1, 5, 9, 1 3] tetraazacyclohexadecine (TAAB ) N, N'-dimethyl formamide(DMF) ruthenium (Ⅱ) complex, [Ru (taab) (DMF )_2]·[ (ClO_4 ...Crystal structure of the title compound, macrocyclic tetrabenzo(b ,f,J, n ) [ 1, 5, 9, 1 3] tetraazacyclohexadecine (TAAB ) N, N'-dimethyl formamide(DMF) ruthenium (Ⅱ) complex, [Ru (taab) (DMF )_2]·[ (ClO_4 )_2](C_(34) H_(34)Cl)2N_6O_(10)Ru , M_r= 874. 66) is monoclinic with space group C2/c and a =36. 689(2) , b=18. 173 (8 ),. c= 10. 666(3)A, β=102. 6(4)°, V=6939. 6 A￣3 , D_c= 1. 67 gcm￣(-3), Z=8. The structural solutions and refinements based on 3183 reflections (I≥3σ(I)) converged at R= 0. 071 , R_w = 0. 074. The TAAB macrocyclic ligand has a saddle-shaped appearance,the ruthenium(Ⅱ) is located on the plane of the four nitrogen atoms of the TAAB with the two perpendicular Ru(Ⅱ)-O bonds coordinated to the DMF molecules.展开更多
In order to interpret the large shift between the observed high spin fraction and the so-called molar high spin fraction in the Mössbauer study on gradual spin transition complexes,numerically we reveal that the ...In order to interpret the large shift between the observed high spin fraction and the so-called molar high spin fraction in the Mössbauer study on gradual spin transition complexes,numerically we reveal that the effects from residual phases in the substance should be considered in the correction by Debye-Waller factors.This result shows that similar Debye-Waller factors in high and low spin states agree well with the conclusion of experimental investigations for such gradual spin transition complexes.展开更多
Three new heterobimetallic acetylene complexes CpNiCo （CO）（PPh） （PhCCH-R-p） [R =H（2）, Br（3）, COCH（4）] have been synthesized in suitable yield （31-47％） via the reaction of（PhCCH-R-p）CO（CO）PPhwith nic...Three new heterobimetallic acetylene complexes CpNiCo （CO）（PPh） （PhCCH-R-p） [R =H（2）, Br（3）, COCH（4）] have been synthesized in suitable yield （31-47％） via the reaction of（PhCCH-R-p）CO（CO）PPhwith nickelcene in n-octane. The complex CpNiCo（CO）（PhC） （1）has also been obtained in 12％ by the reaction of （PhC） Co（CO）with nickelcene. The complexeshave been characterized by elemental analysis, IR andH NMR. Electrochemical study of redoxcouples of these complexes was presented by using cyclic voltammetry on Pt electrodes in acetone.At room temperature, all complexes underwent electrochemically reversible or guasi-reversible one-electron oxidation or reduction to the stable radicals. The radical anions of the complexes couldbe easily detected by ESR method in situ electrolysis in the THF solution. The isotropic parameters,Co= 2.20mT, <g> = 2.052 for the radical anion of complex 1, Co= 2.20 mT, p = 1.42 mT,展开更多
Cyclic voltammetric studies of clusters(C_6H_5-C_2C_6 H_4-R-p)Co_2(CO)_(6-n) L_n[n=0,2; L=PPh_3,P(OEt)_3] and(RCH_2C)_2Co_2(CO_4)(PPh_3)_2 on Pt electrode are described. The primary reduction(0/-1)and oxidation (+1/0)...Cyclic voltammetric studies of clusters(C_6H_5-C_2C_6 H_4-R-p)Co_2(CO)_(6-n) L_n[n=0,2; L=PPh_3,P(OEt)_3] and(RCH_2C)_2Co_2(CO_4)(PPh_3)_2 on Pt electrode are described. The primary reduction(0/-1)and oxidation (+1/0) steps are considered as a mono-electron process for all clusters. For the clusters (C_6H_5C_2C_6H_4-R-P)Co_2(CO)_6, a good linear relation between reduction poten- tial EF_p^(red) and Hammett constant σp of R in the clusters is found. For the clusters(RC_2R′)Co_2(CO)_4L_2, their radical anions are extremely unstable at room temperature and fragment into a series of mono- nuclear species, one of which is(RC-3R′)Co(CO)_2PPh_3. The reaction of radical anions of (RC_2R’)- Co_2(CO)_(6-n) (PPh_3)_n(n=0,2) with PPh_3 also produces mononuclear species (RC_2R’)Co(CO)_2PPh_3 which has been detected by means of cyclic voltammetry and ESR. The influence of R on redox pro- perties of clusters is discussed.展开更多
文摘Two large-pore metal-doped aluminophosphates, Mn4Al5（PO4 ）12[N（ C2H4NH3）3]3 [ N（C2H4NH3）2·（C2H4NH2）]（NH4）2·14H=O（Mn4-NJU） and Co4Al5（PO4）12[N（C2H,NH3）3][N（C2H4NH3）2（C2H4NH2）]3· （ NH4 ）4· 13H2O （ Co4-NJU） , which have the same open framework structures, were hydrothermally synthesized. The structures of these compounds consist of TO4 tetrahedra, which are linked together by corner-sharing to form an open framework with unique intersecting twelve-membered ring channels in three dimensions. The compounds crystallize in cubic space group I（-4）3m with α= 1. 6795（2） nm and V=4. 7374（9） nm^3 for Mn4-NJU, and a=1. 67372（19） nm and V = 4. 6887 （9） nm^3 for Co4-NJU, respectively. Single crystal structure analyses show that the protruding O atoms of the frameworks of the compounds are linked to protonated 4-（ 2-aminoethyl ）diethylenetriamine （TREN, C6H18N4 ） ions in the windows by means of hydrogen-bonding under the hydrothermal condition. It is also found that the components inside the super cages of the compounds are changeable, and the metal ions M^2＋ （M = Mn, Co） and Al^3＋ disorderedly occupy the same crystallographic positions.
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 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Crystal structure of the title compound, macrocyclic tetrabenzo(b ,f,J, n ) [ 1, 5, 9, 1 3] tetraazacyclohexadecine (TAAB ) N, N'-dimethyl formamide(DMF) ruthenium (Ⅱ) complex, [Ru (taab) (DMF )_2]·[ (ClO_4 )_2](C_(34) H_(34)Cl)2N_6O_(10)Ru , M_r= 874. 66) is monoclinic with space group C2/c and a =36. 689(2) , b=18. 173 (8 ),. c= 10. 666(3)A, β=102. 6(4)°, V=6939. 6 A￣3 , D_c= 1. 67 gcm￣(-3), Z=8. The structural solutions and refinements based on 3183 reflections (I≥3σ(I)) converged at R= 0. 071 , R_w = 0. 074. The TAAB macrocyclic ligand has a saddle-shaped appearance,the ruthenium(Ⅱ) is located on the plane of the four nitrogen atoms of the TAAB with the two perpendicular Ru(Ⅱ)-O bonds coordinated to the DMF molecules.
基金Supported by the Visiting Scholarship of Key Laboratory in University and the National Natural Science Foundation of China under Grant Nos.19835050 and 20001004.
文摘In order to interpret the large shift between the observed high spin fraction and the so-called molar high spin fraction in the Mössbauer study on gradual spin transition complexes,numerically we reveal that the effects from residual phases in the substance should be considered in the correction by Debye-Waller factors.This result shows that similar Debye-Waller factors in high and low spin states agree well with the conclusion of experimental investigations for such gradual spin transition complexes.
基金Project supported by the National Natural Science Foundation of China
文摘Three new heterobimetallic acetylene complexes CpNiCo （CO）（PPh） （PhCCH-R-p） [R =H（2）, Br（3）, COCH（4）] have been synthesized in suitable yield （31-47％） via the reaction of（PhCCH-R-p）CO（CO）PPhwith nickelcene in n-octane. The complex CpNiCo（CO）（PhC） （1）has also been obtained in 12％ by the reaction of （PhC） Co（CO）with nickelcene. The complexeshave been characterized by elemental analysis, IR andH NMR. Electrochemical study of redoxcouples of these complexes was presented by using cyclic voltammetry on Pt electrodes in acetone.At room temperature, all complexes underwent electrochemically reversible or guasi-reversible one-electron oxidation or reduction to the stable radicals. The radical anions of the complexes couldbe easily detected by ESR method in situ electrolysis in the THF solution. The isotropic parameters,Co= 2.20mT, <g> = 2.052 for the radical anion of complex 1, Co= 2.20 mT, p = 1.42 mT,
基金This project was supported by the National Natural Science Foundation of China as an item of major project.
文摘Cyclic voltammetric studies of clusters(C_6H_5-C_2C_6 H_4-R-p)Co_2(CO)_(6-n) L_n[n=0,2; L=PPh_3,P(OEt)_3] and(RCH_2C)_2Co_2(CO_4)(PPh_3)_2 on Pt electrode are described. The primary reduction(0/-1)and oxidation (+1/0) steps are considered as a mono-electron process for all clusters. For the clusters (C_6H_5C_2C_6H_4-R-P)Co_2(CO)_6, a good linear relation between reduction poten- tial EF_p^(red) and Hammett constant σp of R in the clusters is found. For the clusters(RC_2R′)Co_2(CO)_4L_2, their radical anions are extremely unstable at room temperature and fragment into a series of mono- nuclear species, one of which is(RC-3R′)Co(CO)_2PPh_3. The reaction of radical anions of (RC_2R’)- Co_2(CO)_(6-n) (PPh_3)_n(n=0,2) with PPh_3 also produces mononuclear species (RC_2R’)Co(CO)_2PPh_3 which has been detected by means of cyclic voltammetry and ESR. The influence of R on redox pro- perties of clusters is discussed.
