The polymerization of acrylonitrile initiated by organolanthanide complexes alone is studied for the first time. The effect of polymerization conditions on catalytic activity of the title complex and molecular weight ...The polymerization of acrylonitrile initiated by organolanthanide complexes alone is studied for the first time. The effect of polymerization conditions on catalytic activity of the title complex and molecular weight of the polymers produced have been studied.展开更多
The coordination complex Sm（C7H5O2）2·（C9H6NO）, synthesized from the reaction of samarium chloride sixhydrate with salicylic acid and 8-hydroxyquinoline, was characterized with IR, elemental analysis, molar co...The coordination complex Sm（C7H5O2）2·（C9H6NO）, synthesized from the reaction of samarium chloride sixhydrate with salicylic acid and 8-hydroxyquinoline, was characterized with IR, elemental analysis, molar conductance, and thermogravimatric analysis. The standard molar enthalpies of solution of [ SmCl3·6H2O （s） ], [ 2C7H6O3 （s） ], [ C9H7NO （ s ） ] and [ Sm （C7H5O3） 2·（ C9H6NO ） （ s ） ] in the calorimetric solvent were determined with the solution-reaction isoperibol calorimeter at 298.15 K to be △sHm^- [ SmCl3·6H2O （s）, 298.15 K ] = - 103.98 ± 0.04 kJ·mol^-1, △sHm^- [2 C7H6O3 （s）, 298.15 K] = 16.35±0.14 kJ·mol^-1,△sHm^-[C9H7NO （s）, 298.15 K] = -6.11±0.08 kJ·mol^-1 and △sHm^-[Sm（C7H5O3）2·（C9H6NO） （s）, 298.15 K] = - 130.08 ± 0.04 kJ·mol^-1, respectively. The enthalpy was determined to be △rHm^- = 89.59 ±0.18 kJ·mol^-1 for the reaction SmCl3·6H2O（s） ＋ 2C7H6O3（s） ＋ C9H7NO（s） = Sm （C7H5O3） 2·（C9H6NO） （ s ） ＋ 3HCl （g） ＋ 6H2O （ l ）. According to the above results and the data given in literature and through Hess＇ law, the standard molar enthalpy of formation of Sin（ C7H5O3 ）2·（C9H7NO）（s） was estimated to be △rHm^- [ Sm （C7H5O3）2·（C9H6NO） （s）, 298.15 K] = - 2055.9 ± 3.03 kJ·mol^-1.展开更多
Phenyl isocyanate was for the first time successfully polymerized by divalent samarium complex (ArO)2Sm(THF)4. The monomer concentration and temperatur affected the polymerization greatly.
The complex of [Sm（p-MOBA）3phen]2 （p-MOBA, p-methoxybenzoate; phen,1 10-phenanthroline） was prepared and characterized by elemental analysis, IR, and UV spectroscopy. The thermal decomposition of the [Sm（p-MOBA）...The complex of [Sm（p-MOBA）3phen]2 （p-MOBA, p-methoxybenzoate; phen,1 10-phenanthroline） was prepared and characterized by elemental analysis, IR, and UV spectroscopy. The thermal decomposition of the [Sm（p-MOBA）sphen]2 complex and its kinetics were studied under a static air atmosphere by TG-DTG methods. The intermediate and residue for each decomposition stage were identified from the TG curve. The kinetic parameters and mecha- nisms of the first decomposition stage were obtained from the analysis of the TG-DTG curves by a new method of processing the data of thermal analysis kinetics. The lifetime equation at a mass loss of 10% was deduced as lnr= - 30.6795 ＋ 21034.56/Tby isothermal thermogravimelric analysis.展开更多
1 Introduction The design and construction of metal-organic polymers has been a field of rapid growth in materials chemistry because of their intriguing topologies and potential applications as functional materials. ...1 Introduction The design and construction of metal-organic polymers has been a field of rapid growth in materials chemistry because of their intriguing topologies and potential applications as functional materials. In this regard, every effort has been devoted to the deliberate design and control of self-assembly infinite coordination networks via selecting the chemistry structures of ligands, Multidentate carboxylate ligands are widely adopted for construction of coordination frameworks due to their rich coordination modes.展开更多
The title complex(C_(11)H_(20)N_3O_6S_3Sm)has been crystallized in triclinic space group P with following unit cell constants: a=8.721(O) ,b=10.468(2) ,c=12.346(8) , =86.39(8) β=71.30(7) γ_=66.77(5) V=970.5(1) ~3...The title complex(C_(11)H_(20)N_3O_6S_3Sm)has been crystallized in triclinic space group P with following unit cell constants: a=8.721(O) ,b=10.468(2) ,c=12.346(8) , =86.39(8) β=71.30(7) γ_=66.77(5) V=970.5(1) ~3,Z=2.The final R factor is 0.040.The coordination number of Samarium atom is nine.The tetraethylene glycol acts as a pentadentate ligand and forms a ringlike structure.展开更多
A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution e...A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔ θ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle...展开更多
A ternary Sm（ Ⅲ ） complex with salicylate （sal-） and o-phenanthroline （phen） was synthesized and incorporated in silica matrix by sol-gel method. The luminescence behavior of the complex in silica gel was studi...A ternary Sm（ Ⅲ ） complex with salicylate （sal-） and o-phenanthroline （phen） was synthesized and incorporated in silica matrix by sol-gel method. The luminescence behavior of the complex in silica gel was studied compared with that of the pure complex by means of emission, excitation spectra and thermogravimetic analysis. The results indicate that the fluorescence intensity ratio of the ^4G5/2→^6H9/2 transition to the ^4G5/2→^6H5/2 transition in silica gel doped with Sm（sal）3 （phen） is lower than that of the pure Sm（sal）3（phen）. The thermal stability of Sm（sal）3（phen） is enhanced greatly by the introduction of the complex into silica matrix. An isolated and chemical inert environment of the complex appears to be responsible for the thermal stability enhancement in silica gel.展开更多
The mixed tris-cyclopentadienyl tetrahydrofuranato samarium complexes bis-(cyclopentadienyl) methylcyclopentadienyl tetrahadrofuranato samarium (Ⅰ) was synthesized by reaction of (C_5H_5)_2SmCl with methyl cyclopenta...The mixed tris-cyclopentadienyl tetrahydrofuranato samarium complexes bis-(cyclopentadienyl) methylcyclopentadienyl tetrahadrofuranato samarium (Ⅰ) was synthesized by reaction of (C_5H_5)_2SmCl with methyl cyclopentadienyl sodium in THF. [(C_5H_5)_2(C_5H_4CH_3)(C_4H_8O)Sm] (Ⅰ) was characterized by elemental analyses, IR spectra and MS spectra. The structure of [(C_5H_5)_2(C_5H_4CH_3)(C_4H_8O)Sm] (Ⅰ), which has two slightly different independent molecules per asymmetric unit, was elucidated through complete X-ray analysis. The crystals are monoclinic with a=1.2791(3) nm, (b=1.0467(2) nm,) c=2.6108(5) nm, β=98.22(2)°, space group Cc, R=0.0381 for 2103 observed reflection with I3σ(I).展开更多
The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF),...The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF), in good yield, which was characterized by elemental analyses, IR, 1H NMR and X ray structural determination. The crystal structure analysis of complex shows that samarium atom is coordinated by two CH 3C 5H 4 groups, one O atom of THF, and N and S atoms from the SC(SPh)NPh ligand to form a distorted trigonal bipyramidal geometry.展开更多
In recent years, there has been considerable inte- rest in complexes formed by lanthanide cations and va-rious benzoate derivatives^[1-4], due to their potential application in areas, such as extraction, separation, g...In recent years, there has been considerable inte- rest in complexes formed by lanthanide cations and va-rious benzoate derivatives^[1-4], due to their potential application in areas, such as extraction, separation, germicide preparation, catalysis, luminescence, and functional material preparation^[5]. As a continuation of the study on lanthanide carboxylate^[6-13], samarium complexes with m-methylbenzoic acid or o-methoxy- benzoic acid and 1,10-phenanthroline were synthesized and characterized by elemental analysis and IR spec- trometry. The thermal decomposition mechanisms of the two complexes were derived and the corresponding non- isothermal kinetics was studied using the Achar diffe- rential method^[14], the MKN integral method^[15], the non-linear isoconversional integral （ NL-INT）, and dif-ferential（NL-DIF） method^[16,17]. The information of the thermodynamic properties of the complex is impor- tant to characterize and understand the properties of the coordination compound, which could eventually be use-ful in determining their potential application.展开更多
The complex of Sm2(o-NBA)6(PHEN)2 (o-NBA, o-Nitrobenzoate; PHEN, 1,10-phenanthroline) was prepar-ed and characterized by elemental analysis, IR and UV spectraoscopy. The thermal decomposition mechanism of Sm2(o-NBA)6(...The complex of Sm2(o-NBA)6(PHEN)2 (o-NBA, o-Nitrobenzoate; PHEN, 1,10-phenanthroline) was prepar-ed and characterized by elemental analysis, IR and UV spectraoscopy. The thermal decomposition mechanism of Sm2(o-NBA)6(PHEN)2 was studied under a static air atmosphere by TG-DTG. The thermal decomposition kinetics of the complex for the first stage was studied under non-isothermal condition. The most probable mechanism functions of the thermal decomposition reaction for the first stage are: G(α)=[-ln(1-α)]1/2, f(α)=2(1-α)[-ln(1-α)]1/2. The activation energy E for the first stage is 259.50 kJ·mol-1, the pre-exponential factor A is 36.19×1018 min-1. The lifetime equation at weight-loss of 10% was deduced as lnτ=-36.70+27 572.12/T by isothermal thermogravimetric analysis.展开更多
文摘The polymerization of acrylonitrile initiated by organolanthanide complexes alone is studied for the first time. The effect of polymerization conditions on catalytic activity of the title complex and molecular weight of the polymers produced have been studied.
基金Project supported by the Hunan Provincial Natural Sciences Foundation of China (03JJY3019)
文摘The coordination complex Sm（C7H5O2）2·（C9H6NO）, synthesized from the reaction of samarium chloride sixhydrate with salicylic acid and 8-hydroxyquinoline, was characterized with IR, elemental analysis, molar conductance, and thermogravimatric analysis. The standard molar enthalpies of solution of [ SmCl3·6H2O （s） ], [ 2C7H6O3 （s） ], [ C9H7NO （ s ） ] and [ Sm （C7H5O3） 2·（ C9H6NO ） （ s ） ] in the calorimetric solvent were determined with the solution-reaction isoperibol calorimeter at 298.15 K to be △sHm^- [ SmCl3·6H2O （s）, 298.15 K ] = - 103.98 ± 0.04 kJ·mol^-1, △sHm^- [2 C7H6O3 （s）, 298.15 K] = 16.35±0.14 kJ·mol^-1,△sHm^-[C9H7NO （s）, 298.15 K] = -6.11±0.08 kJ·mol^-1 and △sHm^-[Sm（C7H5O3）2·（C9H6NO） （s）, 298.15 K] = - 130.08 ± 0.04 kJ·mol^-1, respectively. The enthalpy was determined to be △rHm^- = 89.59 ±0.18 kJ·mol^-1 for the reaction SmCl3·6H2O（s） ＋ 2C7H6O3（s） ＋ C9H7NO（s） = Sm （C7H5O3） 2·（C9H6NO） （ s ） ＋ 3HCl （g） ＋ 6H2O （ l ）. According to the above results and the data given in literature and through Hess＇ law, the standard molar enthalpy of formation of Sin（ C7H5O3 ）2·（C9H7NO）（s） was estimated to be △rHm^- [ Sm （C7H5O3）2·（C9H6NO） （s）, 298.15 K] = - 2055.9 ± 3.03 kJ·mol^-1.
文摘Phenyl isocyanate was for the first time successfully polymerized by divalent samarium complex (ArO)2Sm(THF)4. The monomer concentration and temperatur affected the polymerization greatly.
基金the Natural Science Foundation of Hebei Province (No. B2007000237)Hebei Education Department (No. 2004325)Hebei Normal University (No. L2006Z06, No. L2005Y12).
文摘The complex of [Sm（p-MOBA）3phen]2 （p-MOBA, p-methoxybenzoate; phen,1 10-phenanthroline） was prepared and characterized by elemental analysis, IR, and UV spectroscopy. The thermal decomposition of the [Sm（p-MOBA）sphen]2 complex and its kinetics were studied under a static air atmosphere by TG-DTG methods. The intermediate and residue for each decomposition stage were identified from the TG curve. The kinetic parameters and mecha- nisms of the first decomposition stage were obtained from the analysis of the TG-DTG curves by a new method of processing the data of thermal analysis kinetics. The lifetime equation at a mass loss of 10% was deduced as lnr= - 30.6795 ＋ 21034.56/Tby isothermal thermogravimelric analysis.
基金Supported by the National Natural Science Foundation of China(Nos. 20601007, 50472020 and 20773034)the Natural Science Foundation of Hebei Education Department, China(No.ZH2006002)+1 种基金the Natural Science Foundation of Hebei Province, China(No.B2008000143)the Doctoral Foundation of Hebei Normal University, China(No.103261).
文摘1 Introduction The design and construction of metal-organic polymers has been a field of rapid growth in materials chemistry because of their intriguing topologies and potential applications as functional materials. In this regard, every effort has been devoted to the deliberate design and control of self-assembly infinite coordination networks via selecting the chemistry structures of ligands, Multidentate carboxylate ligands are widely adopted for construction of coordination frameworks due to their rich coordination modes.
文摘The title complex(C_(11)H_(20)N_3O_6S_3Sm)has been crystallized in triclinic space group P with following unit cell constants: a=8.721(O) ,b=10.468(2) ,c=12.346(8) , =86.39(8) β=71.30(7) γ_=66.77(5) V=970.5(1) ~3,Z=2.The final R factor is 0.040.The coordination number of Samarium atom is nine.The tetraethylene glycol acts as a pentadentate ligand and forms a ringlike structure.
基金supported by the National Natural Sciences Foundation of China (20773034)the Natural Science Foundation of Hebei Province (B2007000237)
文摘A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔ θ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle...
基金Project supported bythe Science and Research Planning Project of Zhejiang Provincial Education Department (0424XP18)
文摘A ternary Sm（ Ⅲ ） complex with salicylate （sal-） and o-phenanthroline （phen） was synthesized and incorporated in silica matrix by sol-gel method. The luminescence behavior of the complex in silica gel was studied compared with that of the pure complex by means of emission, excitation spectra and thermogravimetic analysis. The results indicate that the fluorescence intensity ratio of the ^4G5/2→^6H9/2 transition to the ^4G5/2→^6H5/2 transition in silica gel doped with Sm（sal）3 （phen） is lower than that of the pure Sm（sal）3（phen）. The thermal stability of Sm（sal）3（phen） is enhanced greatly by the introduction of the complex into silica matrix. An isolated and chemical inert environment of the complex appears to be responsible for the thermal stability enhancement in silica gel.
文摘The mixed tris-cyclopentadienyl tetrahydrofuranato samarium complexes bis-(cyclopentadienyl) methylcyclopentadienyl tetrahadrofuranato samarium (Ⅰ) was synthesized by reaction of (C_5H_5)_2SmCl with methyl cyclopentadienyl sodium in THF. [(C_5H_5)_2(C_5H_4CH_3)(C_4H_8O)Sm] (Ⅰ) was characterized by elemental analyses, IR spectra and MS spectra. The structure of [(C_5H_5)_2(C_5H_4CH_3)(C_4H_8O)Sm] (Ⅰ), which has two slightly different independent molecules per asymmetric unit, was elucidated through complete X-ray analysis. The crystals are monoclinic with a=1.2791(3) nm, (b=1.0467(2) nm,) c=2.6108(5) nm, β=98.22(2)°, space group Cc, R=0.0381 for 2103 observed reflection with I3σ(I).
文摘The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF), in good yield, which was characterized by elemental analyses, IR, 1H NMR and X ray structural determination. The crystal structure analysis of complex shows that samarium atom is coordinated by two CH 3C 5H 4 groups, one O atom of THF, and N and S atoms from the SC(SPh)NPh ligand to form a distorted trigonal bipyramidal geometry.
基金Supported by the Natural Science Foundation of Hebei Province,China(No.B2007000237)Department of Education of He-bei Pro-vince,China(No.2004325)Hebei Normal University,China(Nos.L2006Z06and L2005Y12).
文摘In recent years, there has been considerable inte- rest in complexes formed by lanthanide cations and va-rious benzoate derivatives^[1-4], due to their potential application in areas, such as extraction, separation, germicide preparation, catalysis, luminescence, and functional material preparation^[5]. As a continuation of the study on lanthanide carboxylate^[6-13], samarium complexes with m-methylbenzoic acid or o-methoxy- benzoic acid and 1,10-phenanthroline were synthesized and characterized by elemental analysis and IR spec- trometry. The thermal decomposition mechanisms of the two complexes were derived and the corresponding non- isothermal kinetics was studied using the Achar diffe- rential method^[14], the MKN integral method^[15], the non-linear isoconversional integral （ NL-INT）, and dif-ferential（NL-DIF） method^[16,17]. The information of the thermodynamic properties of the complex is impor- tant to characterize and understand the properties of the coordination compound, which could eventually be use-ful in determining their potential application.
文摘The complex of Sm2(o-NBA)6(PHEN)2 (o-NBA, o-Nitrobenzoate; PHEN, 1,10-phenanthroline) was prepar-ed and characterized by elemental analysis, IR and UV spectraoscopy. The thermal decomposition mechanism of Sm2(o-NBA)6(PHEN)2 was studied under a static air atmosphere by TG-DTG. The thermal decomposition kinetics of the complex for the first stage was studied under non-isothermal condition. The most probable mechanism functions of the thermal decomposition reaction for the first stage are: G(α)=[-ln(1-α)]1/2, f(α)=2(1-α)[-ln(1-α)]1/2. The activation energy E for the first stage is 259.50 kJ·mol-1, the pre-exponential factor A is 36.19×1018 min-1. The lifetime equation at weight-loss of 10% was deduced as lnτ=-36.70+27 572.12/T by isothermal thermogravimetric analysis.
