The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The...The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).展开更多
A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these c...A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these complexes were also studied.展开更多
Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of...Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.展开更多
Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid (4-SPDA) and 4-(4-(2-(2, 6-dicarboxypyridin-4-yl)- vinyl)styryl)pyridine-2,6-dicarboxylic acid(DSPDA) and their complexes with Tb(Ⅲ) were synthesized and...Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid (4-SPDA) and 4-(4-(2-(2, 6-dicarboxypyridin-4-yl)- vinyl)styryl)pyridine-2,6-dicarboxylic acid(DSPDA) and their complexes with Tb(Ⅲ) were synthesized and characterized by infrared spectrometry, 1H nuclear magnetic resonance, elemental analysis and gas chromatograph-mass spectrometry. The ligand synthetic route was optimized. The fluorescence properties of the complex in solid state, in different kind of solvents and in solutions with different pH values were investigated in detail. The results show that the yields of DSPDA and 4-SPDA reach over 78% by Wittig-Horner reaction and other eight pyridine-2, 6-dicarboxylic acid derivatives with different substituents on pyridine ring, and their complexes with Tb(Ⅲ) are also obtained. The fluorescence intensities of the complexes with electron-donating groups are more intense than those of the complexes with electron-withdrawing groups on pyridine ring; fluorescence intensities of the complexes are the strongest in neutral solution (pH=7), and the less the dipole moment of solvent molecule is, the stronger the fluorescence intensity is. It is found that the two ligands (4-APDA and DSPDA) are the good sensitizers for Tb(Ⅲ) ion.展开更多
Three polymeric erbium(Ⅲ) complexes [Er(oba)(Hoba)(H 2O) 2]H 2O (A),[Er 2(oba) 3(H 2O) 4] (B), [Er 2(oba) 3(2,2′ bpy) 2] (C) (H 2oba=4,4′ oxybis(benzoic acid), 2,2′ bpy = 2,2′ bipyridine) were hydr...Three polymeric erbium(Ⅲ) complexes [Er(oba)(Hoba)(H 2O) 2]H 2O (A),[Er 2(oba) 3(H 2O) 4] (B), [Er 2(oba) 3(2,2′ bpy) 2] (C) (H 2oba=4,4′ oxybis(benzoic acid), 2,2′ bpy = 2,2′ bipyridine) were hydrothermally synthesized by altering the metal/carboxylate ratios or in the presence of an additional chelate 2,2′ bpy ligand, and characterized by single crystal X ray diffraction. The results show that different metal/carboxylate ratios can influence the polymeric structures and the presence of 2,2′ bpy ligand alters the topology of the framework from two dimensional to three dimensional.展开更多
The syntheses, spec(?) complexes are of significance for understanding mechanisms of magnetic interaction between metal ions and the exploitation of the synthesis of molecular magnetic materials. There were a few work...The syntheses, spec(?) complexes are of significance for understanding mechanisms of magnetic interaction between metal ions and the exploitation of the synthesis of molecular magnetic materials. There were a few works reported previously on the syntheses and magnetic in-展开更多
Two new polymeric erbium(Ⅲ) complexes of two flexible double betaine ligands have been synthesized and characterized by X-ray analysis. In {[Er(L1)(H2O)4)Cl3 H2O}n (1) (L1 = 4, 4’ -trimethylenedipyridinio-N, N’-dia...Two new polymeric erbium(Ⅲ) complexes of two flexible double betaine ligands have been synthesized and characterized by X-ray analysis. In {[Er(L1)(H2O)4)Cl3 H2O}n (1) (L1 = 4, 4’ -trimethylenedipyridinio-N, N’-diacetate ), the erbium(Ⅲ) ions form a two-dimensional metal carboxylate layer in which each pair of Er(Ⅲ) atoms is bridged by two syn-anti μ-carboxylato-o,o’ groups, Adjacent layers arecross-linked through hydrogen bonds among aqua ligands, lattice water molecules andchloride ions to form a three-dimensional network. Complex l, C17 H28 N2 O9 ErC13 (Mr =676.0) is monoclinic, space group C2, with a= 27. 408(4), b= 9. 645 (3), c= 9. 423(2) A, p=1loo. 85(1)’, V=2446. 2(9) A’, Z=4, D=l. 836 g/cm’, F(OOO) =1332, μ(MoKa) = 38.06 cm-1, R=0. 048 for 2451 reflections with I>2σ(I). { [Er(L2 ) (H2O)4]Cl3. 5H2O}. (2) (L2=1, 3-bis (pyridinio-4-carboxylato) propane) comprises lanthanide carboxylate chains built from centrosymmetric dimeric units crosslinked by a pair of L2 ligands, discrete anions and lattice water molecules. In the dimeric unit of complex 2, each pair of metal ions is bridged by four syn-syn μ-carboxylatoO, O’ groups that are oriented nearly perpendicular to each other about the metal-metalaxis. The metal carboxylate chains of complex 2 are further cross-linked by hydrogenbonds to form a three-dimensional network. Complex 2, C15 H32 N2O13 ErCl3 (Mr=722.0) belongs to the monoclinic space group C2/m with a=16. 564 (3), b=15. 839(3), c=11. 792(4) , β=122. 27(1)°, V=2616(1), Z=4, Dc=1.833 g/cm3,F(000) =1436, μ (MoKa) = 35. 75 cm-1, R =0.043 for 2436 observed reflectionswithI>2σ(I).展开更多
The self-assembly of 5-bromoisophthalic acid （H2BIPA） with Tb（NO3）3·6H2O under hydrothermal conditions gives rise to a 3D coordination polymer, [Tb2（BIPA）3（CH3CH2OH）]n （1）, which was characterized by el...The self-assembly of 5-bromoisophthalic acid （H2BIPA） with Tb（NO3）3·6H2O under hydrothermal conditions gives rise to a 3D coordination polymer, [Tb2（BIPA）3（CH3CH2OH）]n （1）, which was characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P21/c with a = 19.2591（17）, b = 8.2537（7）, c = 18.5663（17）, β = 104.4720（10）°, V = 2857.6（4）3, C26H15Br3O13Tb2, Mr = 1092.95, Dc = 2.540 g/cm3, F（000） = 2040, μ = 9.173 mm-1 and Z = 4. The final R = 0.0324 and wR = 0.0767 for 5299 observed reflections （I 〉 2σ（I））. Complex 1 displays an unusual three-dimensional （4,6）-connected network with （48.66.8）2（44.62）2（42.84） topology, which is different from [Tb（HBDC）（BDC）（H2O）4]·3.3H2O （BDC = isophthalate） because the -Br substituent of isophthalate results in different electronic effect and steric hindrance to change the coordination modes of carboxylate groups in the assembly process. Moreover, luminescent properties of 1 have also been investigated in the solid state.展开更多
The title complex was synthesised and its molecular and crystal structures were determined by single crystal X ray reflection structure analysis. The crystal data are as follows: K[In Ⅲ(EDTA)(H 2O)]·2H 2O (...The title complex was synthesised and its molecular and crystal structures were determined by single crystal X ray reflection structure analysis. The crystal data are as follows: K[In Ⅲ(EDTA)(H 2O)]·2H 2O (EDTA=ethylene diamine N, N, N′, N′ tetraacetate), Monoclinic, C c space group, a=0.9096(2) nm,b=1.1996(2) nm, c =1.5144(3) nm, β =99.40(3)°, V =1.6302(6) 3, Z =3, D c=1.498 g·cm -3 , μ =1.325 mm -1 , F (000)=726, R =0.0320 and R W=0.0903 for 2315 observed independent reflections. The complex anion [In Ⅲ(EDTA)(H 2O)] - has a seven coordinate pseudo pentagonal bipyramidal (PB D 5h ) structure, in which the EDTA serves as a hexadentate ligand with two N atoms and four O atoms and one water molecule (H 2O) directly coordinated to the central metal ion In Ⅲ as a seventh ligand. 〓〓展开更多
基金Supported by the Natural Science Foundation of Hebei Province(No.2 0 2 140 ) and Hebei Education Departm ent(No.2 0 0 112 1)
文摘The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).
文摘A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these complexes were also studied.
文摘Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.
基金Project(20761002) supported by the National Natural Science Foundation of China
文摘Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid (4-SPDA) and 4-(4-(2-(2, 6-dicarboxypyridin-4-yl)- vinyl)styryl)pyridine-2,6-dicarboxylic acid(DSPDA) and their complexes with Tb(Ⅲ) were synthesized and characterized by infrared spectrometry, 1H nuclear magnetic resonance, elemental analysis and gas chromatograph-mass spectrometry. The ligand synthetic route was optimized. The fluorescence properties of the complex in solid state, in different kind of solvents and in solutions with different pH values were investigated in detail. The results show that the yields of DSPDA and 4-SPDA reach over 78% by Wittig-Horner reaction and other eight pyridine-2, 6-dicarboxylic acid derivatives with different substituents on pyridine ring, and their complexes with Tb(Ⅲ) are also obtained. The fluorescence intensities of the complexes with electron-donating groups are more intense than those of the complexes with electron-withdrawing groups on pyridine ring; fluorescence intensities of the complexes are the strongest in neutral solution (pH=7), and the less the dipole moment of solvent molecule is, the stronger the fluorescence intensity is. It is found that the two ligands (4-APDA and DSPDA) are the good sensitizers for Tb(Ⅲ) ion.
文摘Three polymeric erbium(Ⅲ) complexes [Er(oba)(Hoba)(H 2O) 2]H 2O (A),[Er 2(oba) 3(H 2O) 4] (B), [Er 2(oba) 3(2,2′ bpy) 2] (C) (H 2oba=4,4′ oxybis(benzoic acid), 2,2′ bpy = 2,2′ bipyridine) were hydrothermally synthesized by altering the metal/carboxylate ratios or in the presence of an additional chelate 2,2′ bpy ligand, and characterized by single crystal X ray diffraction. The results show that different metal/carboxylate ratios can influence the polymeric structures and the presence of 2,2′ bpy ligand alters the topology of the framework from two dimensional to three dimensional.
基金Supported by the National Natural Science Foundation of China
文摘The syntheses, spec(?) complexes are of significance for understanding mechanisms of magnetic interaction between metal ions and the exploitation of the synthesis of molecular magnetic materials. There were a few works reported previously on the syntheses and magnetic in-
文摘Two new polymeric erbium(Ⅲ) complexes of two flexible double betaine ligands have been synthesized and characterized by X-ray analysis. In {[Er(L1)(H2O)4)Cl3 H2O}n (1) (L1 = 4, 4’ -trimethylenedipyridinio-N, N’-diacetate ), the erbium(Ⅲ) ions form a two-dimensional metal carboxylate layer in which each pair of Er(Ⅲ) atoms is bridged by two syn-anti μ-carboxylato-o,o’ groups, Adjacent layers arecross-linked through hydrogen bonds among aqua ligands, lattice water molecules andchloride ions to form a three-dimensional network. Complex l, C17 H28 N2 O9 ErC13 (Mr =676.0) is monoclinic, space group C2, with a= 27. 408(4), b= 9. 645 (3), c= 9. 423(2) A, p=1loo. 85(1)’, V=2446. 2(9) A’, Z=4, D=l. 836 g/cm’, F(OOO) =1332, μ(MoKa) = 38.06 cm-1, R=0. 048 for 2451 reflections with I>2σ(I). { [Er(L2 ) (H2O)4]Cl3. 5H2O}. (2) (L2=1, 3-bis (pyridinio-4-carboxylato) propane) comprises lanthanide carboxylate chains built from centrosymmetric dimeric units crosslinked by a pair of L2 ligands, discrete anions and lattice water molecules. In the dimeric unit of complex 2, each pair of metal ions is bridged by four syn-syn μ-carboxylatoO, O’ groups that are oriented nearly perpendicular to each other about the metal-metalaxis. The metal carboxylate chains of complex 2 are further cross-linked by hydrogenbonds to form a three-dimensional network. Complex 2, C15 H32 N2O13 ErCl3 (Mr=722.0) belongs to the monoclinic space group C2/m with a=16. 564 (3), b=15. 839(3), c=11. 792(4) , β=122. 27(1)°, V=2616(1), Z=4, Dc=1.833 g/cm3,F(000) =1436, μ (MoKa) = 35. 75 cm-1, R =0.043 for 2436 observed reflectionswithI>2σ(I).
基金Supported by the National Natural Science Foundation of China (No. 20971004)the Key Project of Chinese Ministry of Education (No. 210102)
文摘The self-assembly of 5-bromoisophthalic acid （H2BIPA） with Tb（NO3）3·6H2O under hydrothermal conditions gives rise to a 3D coordination polymer, [Tb2（BIPA）3（CH3CH2OH）]n （1）, which was characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P21/c with a = 19.2591（17）, b = 8.2537（7）, c = 18.5663（17）, β = 104.4720（10）°, V = 2857.6（4）3, C26H15Br3O13Tb2, Mr = 1092.95, Dc = 2.540 g/cm3, F（000） = 2040, μ = 9.173 mm-1 and Z = 4. The final R = 0.0324 and wR = 0.0767 for 5299 observed reflections （I 〉 2σ（I））. Complex 1 displays an unusual three-dimensional （4,6）-connected network with （48.66.8）2（44.62）2（42.84） topology, which is different from [Tb（HBDC）（BDC）（H2O）4]·3.3H2O （BDC = isophthalate） because the -Br substituent of isophthalate results in different electronic effect and steric hindrance to change the coordination modes of carboxylate groups in the assembly process. Moreover, luminescent properties of 1 have also been investigated in the solid state.
文摘The title complex was synthesised and its molecular and crystal structures were determined by single crystal X ray reflection structure analysis. The crystal data are as follows: K[In Ⅲ(EDTA)(H 2O)]·2H 2O (EDTA=ethylene diamine N, N, N′, N′ tetraacetate), Monoclinic, C c space group, a=0.9096(2) nm,b=1.1996(2) nm, c =1.5144(3) nm, β =99.40(3)°, V =1.6302(6) 3, Z =3, D c=1.498 g·cm -3 , μ =1.325 mm -1 , F (000)=726, R =0.0320 and R W=0.0903 for 2315 observed independent reflections. The complex anion [In Ⅲ(EDTA)(H 2O)] - has a seven coordinate pseudo pentagonal bipyramidal (PB D 5h ) structure, in which the EDTA serves as a hexadentate ligand with two N atoms and four O atoms and one water molecule (H 2O) directly coordinated to the central metal ion In Ⅲ as a seventh ligand. 〓〓
