Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6...Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.展开更多
The dissolving processes,thermochemical properties and thermokinetic parameters of manganese carbohydrazide styph-nate([Mn2(CHZ)2(TNR)2(H2O)4]),nickel carbohydrazide styphnate([Ni(CHZ),(TNR)],)and lead carbohydrazide ...The dissolving processes,thermochemical properties and thermokinetic parameters of manganese carbohydrazide styph-nate([Mn2(CHZ)2(TNR)2(H2O)4]),nickel carbohydrazide styphnate([Ni(CHZ),(TNR)],)and lead carbohydrazide styphnate([Pb_(2)(CHZ)_(2)(TNR)_(2)(H_(2)O)_(2)])in N,N-dimethylformamide(DMF)at 298,15 K were studied by a SETARAM C80 calorime-ter.The results show that the dissolving process of them in DMF are exothermic,however the exothermic peaks are different.The results are associated with the different molecular structure and polarity of solutes.The empirical formulas for the enthalpies of dis-solution(△mH),the relative apparent molar enthalpies(ΦL;),the relative partial molar enthalpies(L,),and the enthalpies of di-lution(△aHt.:)are respectively deduced by polynomial fitting of experimental data.The standard enthalpies of dissolution(Aai H)are calculated respectively as-17.75kJ·mol^(-1),-29.76kJ·mol^(-1)and-15.35 kJ·mol^(-1).The rate constant of dissolution reaction(k),and the reaction order(n)are obtained from the kinetic formulas.展开更多
文摘Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.
基金Technology fund on Applied Physical Chemistry Laboratory(9140C3703051105 and 9140C370303120C37142)State Key Laboratory of Explosion Science and Technology(QNKT12-02)
文摘The dissolving processes,thermochemical properties and thermokinetic parameters of manganese carbohydrazide styph-nate([Mn2(CHZ)2(TNR)2(H2O)4]),nickel carbohydrazide styphnate([Ni(CHZ),(TNR)],)and lead carbohydrazide styphnate([Pb_(2)(CHZ)_(2)(TNR)_(2)(H_(2)O)_(2)])in N,N-dimethylformamide(DMF)at 298,15 K were studied by a SETARAM C80 calorime-ter.The results show that the dissolving process of them in DMF are exothermic,however the exothermic peaks are different.The results are associated with the different molecular structure and polarity of solutes.The empirical formulas for the enthalpies of dis-solution(△mH),the relative apparent molar enthalpies(ΦL;),the relative partial molar enthalpies(L,),and the enthalpies of di-lution(△aHt.:)are respectively deduced by polynomial fitting of experimental data.The standard enthalpies of dissolution(Aai H)are calculated respectively as-17.75kJ·mol^(-1),-29.76kJ·mol^(-1)and-15.35 kJ·mol^(-1).The rate constant of dissolution reaction(k),and the reaction order(n)are obtained from the kinetic formulas.
