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
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
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
New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carb...New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carbazole scaffold have been developed. The markers in complex with Eu<sup>3+</sup> ions possess stability in the aqueous phase, intense and prolonged luminescence (τ 550 - 570 μs) with characteristic emission maxima in the region of 615 nm and excitation wavelengths in the region of 380 - 390 nm, which distinguishes them from most of the analogs used. In the study of marker conjugation with streptavidin, a reagent containing 4 - 5 europium labeling complexes based on spacer-containing carbazole tetraketone was obtained. The marker-doped silicate nanoparticles exhibit intense and long-lived luminescence in the characteristic region.展开更多
A series of neutral nickel complexes featuring N-fluorinated phenyl salicylaldiminato chelate ligands was syn- thesized, and the novel molecular structure of complex C14 was further confirmed by X-ray crystallographic...A series of neutral nickel complexes featuring N-fluorinated phenyl salicylaldiminato chelate ligands was syn- thesized, and the novel molecular structure of complex C14 was further confirmed by X-ray crystallographic analy- sis. The neutral nickel complexes showed high activity up to 9.96× 10^5 g oligomers/（mol Nioh） and high selectivity of C6 in catalyzing ethylene oligomerization using methylaluminoxane （MAO） as cocatalyst. It was observed that the strong electron-withdrawing effect of the fluorinated salicylaldiminato ligand was able to significantly increase the catalytic activity for oligomerization of ethylene. In addition, the influence of reaction parameters such as A1/Ni molar ratio, reaction temperature, a variety of cocatalyst and ethylene pressure on catalytic activity was investigated.展开更多
Treatment of 1,3-diphenyl-1,3-propanedione 1a with europium (III) chloride in the presence of piperidine results in the halide ligands exchange giving newly piperidinium tetrakis (1,3-diphenyl-1,3-propanedionato)europ...Treatment of 1,3-diphenyl-1,3-propanedione 1a with europium (III) chloride in the presence of piperidine results in the halide ligands exchange giving newly piperidinium tetrakis (1,3-diphenyl-1,3-propanedionato)europate(III) complex 2a. The complex was characterized by 1H-NMR, positive FAB-mass, and Elemental Analysis. The exact molecular structure of 2a was determined by single crystal X-ray diffraction with the monoclinic space group Cc (centrosymmetric, No.13). The large cavity sizes of the complex 2a facilitated the inclusion of water and benzene solvate molecules. The other two different crystals 2b, 2c having two water molecules and one benzene moleculewere obtained by the crystallization in different solvents and the exact molecular structures were determined by single crystal X-ray diffraction analysis with space groups P21/n (centrosymmetric, No.14), and P21/n (centrosymmetric, No.14), respectively. The eight coordinate structures of the complexes in the three crystals were slightly different due to the crystal packing and the existence of the solvent molecule(s). The photoluminescence studies indicated that four β-diketone ligands acted as strong antenna ligands and transferred the absorbed energy to europium (III) ion, consequently red luminescence was observed. These strong emissions wereattributed to the 5D0 → 7F2 transition of Europium (III) ions under UV excitation. The photoluminescence spectrum of the three crystals was almost same in solid as well as in solution.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
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.
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...
文摘New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carbazole scaffold have been developed. The markers in complex with Eu<sup>3+</sup> ions possess stability in the aqueous phase, intense and prolonged luminescence (τ 550 - 570 μs) with characteristic emission maxima in the region of 615 nm and excitation wavelengths in the region of 380 - 390 nm, which distinguishes them from most of the analogs used. In the study of marker conjugation with streptavidin, a reagent containing 4 - 5 europium labeling complexes based on spacer-containing carbazole tetraketone was obtained. The marker-doped silicate nanoparticles exhibit intense and long-lived luminescence in the characteristic region.
基金Acknowledgement The authors gratefully acknowledge the financial support subsidized by the National Basic Research Program of China （No. 2005CB623800）, the National Natural Science Foundation of China （NNSFC） （No. 21072128）.
文摘A series of neutral nickel complexes featuring N-fluorinated phenyl salicylaldiminato chelate ligands was syn- thesized, and the novel molecular structure of complex C14 was further confirmed by X-ray crystallographic analy- sis. The neutral nickel complexes showed high activity up to 9.96× 10^5 g oligomers/（mol Nioh） and high selectivity of C6 in catalyzing ethylene oligomerization using methylaluminoxane （MAO） as cocatalyst. It was observed that the strong electron-withdrawing effect of the fluorinated salicylaldiminato ligand was able to significantly increase the catalytic activity for oligomerization of ethylene. In addition, the influence of reaction parameters such as A1/Ni molar ratio, reaction temperature, a variety of cocatalyst and ethylene pressure on catalytic activity was investigated.
文摘Treatment of 1,3-diphenyl-1,3-propanedione 1a with europium (III) chloride in the presence of piperidine results in the halide ligands exchange giving newly piperidinium tetrakis (1,3-diphenyl-1,3-propanedionato)europate(III) complex 2a. The complex was characterized by 1H-NMR, positive FAB-mass, and Elemental Analysis. The exact molecular structure of 2a was determined by single crystal X-ray diffraction with the monoclinic space group Cc (centrosymmetric, No.13). The large cavity sizes of the complex 2a facilitated the inclusion of water and benzene solvate molecules. The other two different crystals 2b, 2c having two water molecules and one benzene moleculewere obtained by the crystallization in different solvents and the exact molecular structures were determined by single crystal X-ray diffraction analysis with space groups P21/n (centrosymmetric, No.14), and P21/n (centrosymmetric, No.14), respectively. The eight coordinate structures of the complexes in the three crystals were slightly different due to the crystal packing and the existence of the solvent molecule(s). The photoluminescence studies indicated that four β-diketone ligands acted as strong antenna ligands and transferred the absorbed energy to europium (III) ion, consequently red luminescence was observed. These strong emissions wereattributed to the 5D0 → 7F2 transition of Europium (III) ions under UV excitation. The photoluminescence spectrum of the three crystals was almost same in solid as well as in solution.
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.
