Two novel pyridine-2,6-dicarboxylic acid derivatives of mono-β-diketone named methyl 6-biphenylacetyl-2-pyridinecarboxylate (MBP) and 6-biphenylacetyl-2-pyridinecarboxylic acid (BAA) and their corresponding binary co...Two novel pyridine-2,6-dicarboxylic acid derivatives of mono-β-diketone named methyl 6-biphenylacetyl-2-pyridinecarboxylate (MBP) and 6-biphenylacetyl-2-pyridinecarboxylic acid (BAA) and their corresponding binary complexes Tb(MBP)3.6H2O and Tb(BAA)3·6H2O were synthesized. The ligands were characterized by elemental analysis, FT-IR and 1H-NMR, and the complexes were characterized with elemental analysis, FT-IR, 1H-NMR and thermogravimetric and differential thermal analysis(TG-DTA). The investigation of fluo...展开更多
A novel carbazole functionalized β-diketone, methyl 6-（9-ethylcarbazole-3-yl）-oxoacetyl-2-pyridinecarboxylate （MEP）, and its corresponding binary Eu（III） complexes Eu（MEP）y2H2O and ternary complex Eu（MEP）aP...A novel carbazole functionalized β-diketone, methyl 6-（9-ethylcarbazole-3-yl）-oxoacetyl-2-pyridinecarboxylate （MEP）, and its corresponding binary Eu（III） complexes Eu（MEP）y2H2O and ternary complex Eu（MEP）aPhen with 1,10-Phenanthroline （Phen） were prepared. The ligand was characterized based on elemental analysis, FT-IR, and ^1H NMR, and the complexes were characterized with elemental analysis, FT-IR and thermogravimetric and differential thermal analysis （TG-DTA）. The investigation of fluorescence properties of the complexes Eu（MEP）3·2H2O and Eu（MEP）3Phen showed that the Eu（III） ion could be sensitized efficiently by the ligand to some extent, in partitular, in the ternary system, the secondary ligand Phen acting as a light-harvesting center was involved in the highly efficient energy transfer process, and the emission was stronger than the binary complex. In addition, the introduction of the carbazole moiety enlarged the n-conjugated system of the ligand and enhanced the luminescent intensity of the complexes.展开更多
Two kinds of fishbone-like, β-diketone-based liquid crystalline polysilsesquioxanes(FBDKLCP'S), homopolymeric (H-FBDKLCP) and copolymeric (C-FBDKaLCP) have been first synthesized via the hydrosilylation reaction ...Two kinds of fishbone-like, β-diketone-based liquid crystalline polysilsesquioxanes(FBDKLCP'S), homopolymeric (H-FBDKLCP) and copolymeric (C-FBDKaLCP) have been first synthesized via the hydrosilylation reaction of a vinyl-terminated β-diketone with the homopolymeric ladderlike polyhydrosilsesquioxane (LPHSQ) and random copolymethylhydrosilsesquioxane (LRPMHSQ) respectively. These new kinds of FBDKLCP with M of 10~4 is thermotroic liquid crystalline polymer and its clearing temperatures T_i's and mesophase range △T's are much higher than those of the corresponding comb-like β-diketone liquid crystalline polysiloxane (DKLCP) by about 200℃. Similar results have been observed with the comparison of the two different structure Cu-coordinating compounds The significant increases in T_((?))'s and △T's of the FBDKLCP and Cu-FBDKLCP are mainly attributed to the great rigidity of the ladderlike polysilsesquioxane backbone.展开更多
Water-caused luminescence quenching is a well-known and intractable issue for luminescence lanthanide complexes, greatly confining their broad application as sensing and displaying devices in water system.Herein, an a...Water-caused luminescence quenching is a well-known and intractable issue for luminescence lanthanide complexes, greatly confining their broad application as sensing and displaying devices in water system.Herein, an anionic and coordination-saturated lanthanide complex with a nanosheet-like structure has been prepared. It exhibits excellent photophysical properties both in solid state and in aqueous suspension. Noteworthily, a 13% improvement for sensitization efficiency from organic ligand to central lanthanide ion has been realized, indicating an exceptional phenomenon of water-induced luminescence improvement which is rarely reported previously. Moreover, the aqueous suspension of as-prepared luminophore could act as a chemo-sensor responding to various organic solvents in water. Both of waterinduced luminescence improvement and extended sensing behavior in this work provide a new platform for developing highly performant and practical luminescent materials in the water system.展开更多
The strong photoluminescence properties of europium complexes with organic ligands attracted the attention of many researchers and found a wide range of uses in medical, industrial and biological fields. In this artic...The strong photoluminescence properties of europium complexes with organic ligands attracted the attention of many researchers and found a wide range of uses in medical, industrial and biological fields. In this article, four new Tetrakis europium complexes <b>3a</b>, <b>3b</b>, <b>3c</b> and <b>3d</b> have been prepared using 1-phenyl-4,4,4-trifluoro-1,3-butenedionato ligand and pyridinium, bipyridinium, piperazinium and piperidinium counter cations. These complexes have been characterized by negative FAB-mass. The crystal structures of <b>3a</b>, <b>3b</b>, <b>3c</b> and <b>3d</b> were determined by single crystal X-ray diffraction analysis. The complex <b>3a</b> crystallized in monoclinic form, space group <i>P</i>2<sub>1</sub>/<i>n </i><span>with four molecules in the unit cell.<i> </i>The complex <b>3b</b> crystallized in monoclinic form, space group <i>P</i>2/<i>n </i><span>with two complex molecules in the unit cell.<i> </i>The complex <b>3c</b> crystallized in monoclinic form, space group <i>C</i>2/<i>c </i><span>with sixteen molecules in the unit cell.<i> </i>The complex <b>3d</b> crystallized in monoclinic form, space group <i>P</i>2<sub>1</sub>/<i>n </i><span>with four complex molecules in the unit cell. The complex <b>3a</b> has 1,2-alternative structure, <b>3b</b> has 1,3-alternative structure, <b>3c </b>has cone like structure and <b>3d</b> has partial cone like structure. The photoluminescence properties of these complexes have been evaluated. Strong red emissions were observed in all four complexes due to <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>2</sub> transition of Europium (III) ions under UV excitation. Four <i>β</i>-diketone ligands acted as strong antenna ligands and transferred the absorbed energy to europium (III) ion effectively;consequently strong red luminescence was observed.展开更多
以N-乙基-3-吲哚三氟甲基β-二酮(EIFD)为主配体,分别以乙二醇单甲醚(EM)、乙二醇二甲醚(EDM)、二缩三乙二醇(TEG)为辅助配体,与DyCl3·6H2O反应合成了一系列Dy(Ⅲ)配合物[Dy(EIFD)3(EM)]·CH2Cl2(1)、[Dy(EIFD)3(EDM)]·CH...以N-乙基-3-吲哚三氟甲基β-二酮(EIFD)为主配体,分别以乙二醇单甲醚(EM)、乙二醇二甲醚(EDM)、二缩三乙二醇(TEG)为辅助配体,与DyCl3·6H2O反应合成了一系列Dy(Ⅲ)配合物[Dy(EIFD)3(EM)]·CH2Cl2(1)、[Dy(EIFD)3(EDM)]·CH2Cl2(2)和[Dy(EIFD)3(TEG)](3)。X射线单晶衍射分析表明,3个配合物都是八配位的单核结构,配位构型分别为双帽三棱柱、正十二面体和双帽三棱柱,分别具有C2v、D2d和C2v对称性。磁学性质显示了配合物1~3具有慢弛豫现象,能垒分别为95.1 K (1)、40.5 K (2)、53.8和13.4 K (3),且配合物1和3有明显的蝴蝶状磁滞回线。进一步讨论了配合物中Dy-O键长和含氧辅助配体的电子效应对配合物有效翻转能垒的影响。展开更多
基金Project supported by the Science Foundation of Hunan Province (05JT1022)
文摘Two novel pyridine-2,6-dicarboxylic acid derivatives of mono-β-diketone named methyl 6-biphenylacetyl-2-pyridinecarboxylate (MBP) and 6-biphenylacetyl-2-pyridinecarboxylic acid (BAA) and their corresponding binary complexes Tb(MBP)3.6H2O and Tb(BAA)3·6H2O were synthesized. The ligands were characterized by elemental analysis, FT-IR and 1H-NMR, and the complexes were characterized with elemental analysis, FT-IR, 1H-NMR and thermogravimetric and differential thermal analysis(TG-DTA). The investigation of fluo...
基金supported by China Postdoctoral Science Foundation (20080431027)the Postdoctoral Science Foundation of Central South University (50573019)
文摘A novel carbazole functionalized β-diketone, methyl 6-（9-ethylcarbazole-3-yl）-oxoacetyl-2-pyridinecarboxylate （MEP）, and its corresponding binary Eu（III） complexes Eu（MEP）y2H2O and ternary complex Eu（MEP）aPhen with 1,10-Phenanthroline （Phen） were prepared. The ligand was characterized based on elemental analysis, FT-IR, and ^1H NMR, and the complexes were characterized with elemental analysis, FT-IR and thermogravimetric and differential thermal analysis （TG-DTA）. The investigation of fluorescence properties of the complexes Eu（MEP）3·2H2O and Eu（MEP）3Phen showed that the Eu（III） ion could be sensitized efficiently by the ligand to some extent, in partitular, in the ternary system, the secondary ligand Phen acting as a light-harvesting center was involved in the highly efficient energy transfer process, and the emission was stronger than the binary complex. In addition, the introduction of the carbazole moiety enlarged the n-conjugated system of the ligand and enhanced the luminescent intensity of the complexes.
文摘Two kinds of fishbone-like, β-diketone-based liquid crystalline polysilsesquioxanes(FBDKLCP'S), homopolymeric (H-FBDKLCP) and copolymeric (C-FBDKaLCP) have been first synthesized via the hydrosilylation reaction of a vinyl-terminated β-diketone with the homopolymeric ladderlike polyhydrosilsesquioxane (LPHSQ) and random copolymethylhydrosilsesquioxane (LRPMHSQ) respectively. These new kinds of FBDKLCP with M of 10~4 is thermotroic liquid crystalline polymer and its clearing temperatures T_i's and mesophase range △T's are much higher than those of the corresponding comb-like β-diketone liquid crystalline polysiloxane (DKLCP) by about 200℃. Similar results have been observed with the comparison of the two different structure Cu-coordinating compounds The significant increases in T_((?))'s and △T's of the FBDKLCP and Cu-FBDKLCP are mainly attributed to the great rigidity of the ladderlike polysilsesquioxane backbone.
基金National Natural Science Foundation of China (No.22075071)Reform and Development Fund Project of Local University supported by the Central Government。
文摘Water-caused luminescence quenching is a well-known and intractable issue for luminescence lanthanide complexes, greatly confining their broad application as sensing and displaying devices in water system.Herein, an anionic and coordination-saturated lanthanide complex with a nanosheet-like structure has been prepared. It exhibits excellent photophysical properties both in solid state and in aqueous suspension. Noteworthily, a 13% improvement for sensitization efficiency from organic ligand to central lanthanide ion has been realized, indicating an exceptional phenomenon of water-induced luminescence improvement which is rarely reported previously. Moreover, the aqueous suspension of as-prepared luminophore could act as a chemo-sensor responding to various organic solvents in water. Both of waterinduced luminescence improvement and extended sensing behavior in this work provide a new platform for developing highly performant and practical luminescent materials in the water system.
文摘The strong photoluminescence properties of europium complexes with organic ligands attracted the attention of many researchers and found a wide range of uses in medical, industrial and biological fields. In this article, four new Tetrakis europium complexes <b>3a</b>, <b>3b</b>, <b>3c</b> and <b>3d</b> have been prepared using 1-phenyl-4,4,4-trifluoro-1,3-butenedionato ligand and pyridinium, bipyridinium, piperazinium and piperidinium counter cations. These complexes have been characterized by negative FAB-mass. The crystal structures of <b>3a</b>, <b>3b</b>, <b>3c</b> and <b>3d</b> were determined by single crystal X-ray diffraction analysis. The complex <b>3a</b> crystallized in monoclinic form, space group <i>P</i>2<sub>1</sub>/<i>n </i><span>with four molecules in the unit cell.<i> </i>The complex <b>3b</b> crystallized in monoclinic form, space group <i>P</i>2/<i>n </i><span>with two complex molecules in the unit cell.<i> </i>The complex <b>3c</b> crystallized in monoclinic form, space group <i>C</i>2/<i>c </i><span>with sixteen molecules in the unit cell.<i> </i>The complex <b>3d</b> crystallized in monoclinic form, space group <i>P</i>2<sub>1</sub>/<i>n </i><span>with four complex molecules in the unit cell. The complex <b>3a</b> has 1,2-alternative structure, <b>3b</b> has 1,3-alternative structure, <b>3c </b>has cone like structure and <b>3d</b> has partial cone like structure. The photoluminescence properties of these complexes have been evaluated. Strong red emissions were observed in all four complexes due to <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>2</sub> transition of Europium (III) ions under UV excitation. Four <i>β</i>-diketone ligands acted as strong antenna ligands and transferred the absorbed energy to europium (III) ion effectively;consequently strong red luminescence was observed.
文摘以N-乙基-3-吲哚三氟甲基β-二酮(EIFD)为主配体,分别以乙二醇单甲醚(EM)、乙二醇二甲醚(EDM)、二缩三乙二醇(TEG)为辅助配体,与DyCl3·6H2O反应合成了一系列Dy(Ⅲ)配合物[Dy(EIFD)3(EM)]·CH2Cl2(1)、[Dy(EIFD)3(EDM)]·CH2Cl2(2)和[Dy(EIFD)3(TEG)](3)。X射线单晶衍射分析表明,3个配合物都是八配位的单核结构,配位构型分别为双帽三棱柱、正十二面体和双帽三棱柱,分别具有C2v、D2d和C2v对称性。磁学性质显示了配合物1~3具有慢弛豫现象,能垒分别为95.1 K (1)、40.5 K (2)、53.8和13.4 K (3),且配合物1和3有明显的蝴蝶状磁滞回线。进一步讨论了配合物中Dy-O键长和含氧辅助配体的电子效应对配合物有效翻转能垒的影响。
