The metal complexes of polyaza cryptand have attracted much attentionowing to their special structure, unusual photo-chemical, electrical and catalyticproperties. Recently, Lehn and Nelson synthesized successively a ... The metal complexes of polyaza cryptand have attracted much attentionowing to their special structure, unusual photo-chemical, electrical and catalyticproperties. Recently, Lehn and Nelson synthesized successively a series ofcryptands and crypatates with high yield by (2+3) schiff-base condensation of tris(2-aminoethyl)amine and aryl dialdehyde. But so far, little work about the analogueswith larger cavities and flexible chains condensed by tris (3-aminopropyl) amine (abbr.展开更多
New alkaline earth metal cryptates [ML]（NO3）2 ·2H2O （M=Ca^2＋, Sr^2＋, Ba^2＋; L = 1, 4,12,15,18, 26, 31, 39, 42, 43, 44-undecaazapentacyclo- [ 13.13.13.1^6,10 .1^20,24 .1^33,37 ]-tetratetraconta -4, 6, 8, 10...New alkaline earth metal cryptates [ML]（NO3）2 ·2H2O （M=Ca^2＋, Sr^2＋, Ba^2＋; L = 1, 4,12,15,18, 26, 31, 39, 42, 43, 44-undecaazapentacyclo- [ 13.13.13.1^6,10 .1^20,24 .1^33,37 ]-tetratetraconta -4, 6, 8, 10（44）, 11, 18, 20, 22, 24（43）, 25, 31, 33, 35, 37（42）, 38-pentadecaene） were synthesized by [2 ＋ 3 ] template condensation of tris（2-aminoethyl） amine with 2, 6-diformylpyridine, and then by transmetallation reactions of the calcium cryptate [CaL] （NO3）2·2H2O with corresponding lanthanide ions; three lanthanide cryptates [ LnL] （NO）3·3H2O （Ln = Eu, Gd, Tb） were synthesized and characterized by physical methods. The crystal structure of the terbium cryptate [TbL] （NO）3·3H2O was studied by X-ray analysis. The central atom was coordinated by three pyridyl and six imino nitrogen atoms and exhibited a distorted tricapped trigonal prismatic coordination geometry.展开更多
The mononuclear cryptate [Eu(H 3L F)(NO 3)(H 2O)](NO 3) 2 and the heterodinuclear cryptate [EuZnL F(DMF)](ClO 4) 2 were synthesized and characterized. The triplet state energy of the cryptand (H 3L F) was ...The mononuclear cryptate [Eu(H 3L F)(NO 3)(H 2O)](NO 3) 2 and the heterodinuclear cryptate [EuZnL F(DMF)](ClO 4) 2 were synthesized and characterized. The triplet state energy of the cryptand (H 3L F) was studied by phosphorescence spectrum. The fluorescent properties of Eu(Ⅲ) cryptates in MeOH solution show that the cryptand (H 3L F) can sensitize the Eu(Ⅲ) ion to luminescence and the introduction of the Zn(Ⅱ) ion into the mononuclear Eu(Ⅲ) cryptate resulted in blue shift of three ligand centered bands, increase of molar absorption coefficient and increase of the luminescence intensity of Eu(Ⅲ).展开更多
A new mononuclear cadmium（Ⅱ） cryptate has been synthesized by [2＋3] Schiff base condensation of tri（2-aminoethyl）amine with glyoxal in the presence of Cd（ClO4）2·6H2O. The crystal structure, spectral chara...A new mononuclear cadmium（Ⅱ） cryptate has been synthesized by [2＋3] Schiff base condensation of tri（2-aminoethyl）amine with glyoxal in the presence of Cd（ClO4）2·6H2O. The crystal structure, spectral characterization and molar conductivity show that cadmium（Ⅱ） is sixcoordinated （N6） into a distorted octahedral geometry.展开更多
The crystal structure of cryptand L was determined via X-ray diffraction analysis.Four solid(cryptates) of cryptand(L) with M(Ⅲ) nitrates(M=Sm,Eu,Tb,Dy) were prepared and characterized by means of fluorescence spectr...The crystal structure of cryptand L was determined via X-ray diffraction analysis.Four solid(cryptates) of cryptand(L) with M(Ⅲ) nitrates(M=Sm,Eu,Tb,Dy) were prepared and characterized by means of fluorescence spectroscopy.The fluorescence properties of those complexes show that all the cryptates have stronger luminescence intensity.That the complex of Eu(Ⅲ) has the strongest luminescence intensity(among) them shows that the cryptand′s triplet state energy matches with the vibration energy level of Eu(Ⅲ).The difference between fluorescence intensities of L cryptates and other series of cryptates implies that the (energy) transfer from L is more effective in fluorescence and antenna when L has a more flexibility structure.展开更多
以2,6-二甲基吡啶-3,5-二甲酸二乙酯为起始原料,经N-溴代丁二酰亚胺(NBS)溴代、亲电取代反应合成了时间分辨荧光免疫分析双功能螯合剂2,6-{N,N′,N,N′-[二(2,2′-联吡啶-6,6′-二甲基)]二(氨甲基)}-吡啶-3,5-二羧酸二乙酯。经差热分析...以2,6-二甲基吡啶-3,5-二甲酸二乙酯为起始原料,经N-溴代丁二酰亚胺(NBS)溴代、亲电取代反应合成了时间分辨荧光免疫分析双功能螯合剂2,6-{N,N′,N,N′-[二(2,2′-联吡啶-6,6′-二甲基)]二(氨甲基)}-吡啶-3,5-二羧酸二乙酯。经差热分析仪(DTA)、傅里叶变换红外光谱仪(FTIR)、核磁共振波谱仪(1 H NMR)、质谱仪(MS)等技术手段表征确认了化合物结构和性能。对该化合物与铕离子形成螯合物的荧光性质研究表明:激发光谱波长范围较宽,激发峰值为322nm;荧光发射峰为597nm(~5D_0-~7F_1)、618nm(~5D_0-~7F_2);荧光寿命为918μs;量子产率Φ=0.249。展开更多
基金Project supported by the National Natural Science Foundation of China and Fuzhou State Key Laboratory of Structural Chemistry.
文摘 The metal complexes of polyaza cryptand have attracted much attentionowing to their special structure, unusual photo-chemical, electrical and catalyticproperties. Recently, Lehn and Nelson synthesized successively a series ofcryptands and crypatates with high yield by (2+3) schiff-base condensation of tris(2-aminoethyl)amine and aryl dialdehyde. But so far, little work about the analogueswith larger cavities and flexible chains condensed by tris (3-aminopropyl) amine (abbr.
基金Project supported by the National Natural Science Foundation of China (20671075)the Natural Science Foundation of Hubei Province (2005ABA021)China Postdoctoral Science Foundation (20060390858)
文摘New alkaline earth metal cryptates [ML]（NO3）2 ·2H2O （M=Ca^2＋, Sr^2＋, Ba^2＋; L = 1, 4,12,15,18, 26, 31, 39, 42, 43, 44-undecaazapentacyclo- [ 13.13.13.1^6,10 .1^20,24 .1^33,37 ]-tetratetraconta -4, 6, 8, 10（44）, 11, 18, 20, 22, 24（43）, 25, 31, 33, 35, 37（42）, 38-pentadecaene） were synthesized by [2 ＋ 3 ] template condensation of tris（2-aminoethyl） amine with 2, 6-diformylpyridine, and then by transmetallation reactions of the calcium cryptate [CaL] （NO3）2·2H2O with corresponding lanthanide ions; three lanthanide cryptates [ LnL] （NO）3·3H2O （Ln = Eu, Gd, Tb） were synthesized and characterized by physical methods. The crystal structure of the terbium cryptate [TbL] （NO）3·3H2O was studied by X-ray analysis. The central atom was coordinated by three pyridyl and six imino nitrogen atoms and exhibited a distorted tricapped trigonal prismatic coordination geometry.
文摘The mononuclear cryptate [Eu(H 3L F)(NO 3)(H 2O)](NO 3) 2 and the heterodinuclear cryptate [EuZnL F(DMF)](ClO 4) 2 were synthesized and characterized. The triplet state energy of the cryptand (H 3L F) was studied by phosphorescence spectrum. The fluorescent properties of Eu(Ⅲ) cryptates in MeOH solution show that the cryptand (H 3L F) can sensitize the Eu(Ⅲ) ion to luminescence and the introduction of the Zn(Ⅱ) ion into the mononuclear Eu(Ⅲ) cryptate resulted in blue shift of three ligand centered bands, increase of molar absorption coefficient and increase of the luminescence intensity of Eu(Ⅲ).
基金This project was supported by the National Natural Science Foundation of China (No. 50372028) and the Foundation of hhit Marine-Technology lab
文摘A new mononuclear cadmium（Ⅱ） cryptate has been synthesized by [2＋3] Schiff base condensation of tri（2-aminoethyl）amine with glyoxal in the presence of Cd（ClO4）2·6H2O. The crystal structure, spectral characterization and molar conductivity show that cadmium（Ⅱ） is sixcoordinated （N6） into a distorted octahedral geometry.
文摘New lanthanide cryptates [LnL](ClO_4)_3 (Ln=Eu 3+, Ce 3+, Pr 3+, Sm 3+, Gd 3+, Tb 3+; L=1, 4, 12, 15, 18, 26, 31, 39, 42, 43, 44-undecaazapentacyclo-[13.13.13.1 6, 10.1 20, 24.1 33, 37]-tetratetraconta-4, 6, 8, 10(44), 11, 18, 20, 22, 24(43), 25, 31, 33, 35, 37(42), 38-penta decaene) were synthesized by transmetalation reaction of lanthanide perchlorates with its barium cryptate which was obtained by [2+3] template condensation of tren with 2,6-diformylpyridine in the presence of barium perchlorate, and characterized by elemental analysis, IR and electrospray mass spectrum.
文摘The crystal structure of cryptand L was determined via X-ray diffraction analysis.Four solid(cryptates) of cryptand(L) with M(Ⅲ) nitrates(M=Sm,Eu,Tb,Dy) were prepared and characterized by means of fluorescence spectroscopy.The fluorescence properties of those complexes show that all the cryptates have stronger luminescence intensity.That the complex of Eu(Ⅲ) has the strongest luminescence intensity(among) them shows that the cryptand′s triplet state energy matches with the vibration energy level of Eu(Ⅲ).The difference between fluorescence intensities of L cryptates and other series of cryptates implies that the (energy) transfer from L is more effective in fluorescence and antenna when L has a more flexibility structure.
基金Supported by the Program for New Century Excellent Talents in University of Henan Province(2005HANCET-02)the Natural Science Foundation of Henan Province,the Program for Training Young Excellent Cadreman Teachers in University of Henan Province,the Stress Founda-tion of Henan University(05ZDZR002)
文摘以2,6-二甲基吡啶-3,5-二甲酸二乙酯为起始原料,经N-溴代丁二酰亚胺(NBS)溴代、亲电取代反应合成了时间分辨荧光免疫分析双功能螯合剂2,6-{N,N′,N,N′-[二(2,2′-联吡啶-6,6′-二甲基)]二(氨甲基)}-吡啶-3,5-二羧酸二乙酯。经差热分析仪(DTA)、傅里叶变换红外光谱仪(FTIR)、核磁共振波谱仪(1 H NMR)、质谱仪(MS)等技术手段表征确认了化合物结构和性能。对该化合物与铕离子形成螯合物的荧光性质研究表明:激发光谱波长范围较宽,激发峰值为322nm;荧光发射峰为597nm(~5D_0-~7F_1)、618nm(~5D_0-~7F_2);荧光寿命为918μs;量子产率Φ=0.249。
