The protonation constants of a new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, BDBPH, were determined by potentiometric measurement at 25.0 degreesC and mu = 0.100 mol.L-1 (KCl). The species distribut...The protonation constants of a new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, BDBPH, were determined by potentiometric measurement at 25.0 degreesC and mu = 0.100 mol.L-1 (KCl). The species distributions of the deprotonated and protonated compounds in the pH range from 2 to 12 aqueous solutions were also described.展开更多
A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesi...A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesized by the NaBH4 reduction of the Schiff-base obtained from the [2+2] condensation between diethylenetriamine and diformyl -p-cresol. The structure was characterized by elemental analysis, 1HNMR and FAB-MS. The synthetic method was also discussed.展开更多
The hexahydro\|bromide salt of a new 24\|membered hexaaza diphenol macrocyclic ligand, （H6BDBPH）Br6·4H2O （C 26H 56N6O6Br6, Mr= 1028.23）, crystallizes in the monoclinic system, space group P21/c, with cell par...The hexahydro\|bromide salt of a new 24\|membered hexaaza diphenol macrocyclic ligand, （H6BDBPH）Br6·4H2O （C 26H 56N6O6Br6, Mr= 1028.23）, crystallizes in the monoclinic system, space group P21/c, with cell parameters: a=14.441（5）, b=11.482（4）, c=12.090（6）, β=96.92°, V= 1990 （1）3, Z=2, Dc=1.716 g/cm3; F（000） =1024. MoKα radiation, λ= 0.71013), R = 0.0643 and wR = 0.1356 for 3507 independent reflections with I>2σ（I）. The macrocyclic ligand adapts chair form, and the crystallographic inversion center is located in the macrocyclic cavity, and the six bromide ions and four water molecules are situated symmetrically outside the macrocyclic cavity.展开更多
The intramolecular hydrogen bond self-template effect was suggested in the process of directly synthesizing the first six chiral metal-free Robson-type macrocyclic ligands. These ligands were characterized by H-1 NMR,...The intramolecular hydrogen bond self-template effect was suggested in the process of directly synthesizing the first six chiral metal-free Robson-type macrocyclic ligands. These ligands were characterized by H-1 NMR, IR, FAB-MS.展开更多
The coordination complex of Co（Ⅲ） based on a macrocyclic triamine ligand 1,4-diacetate-1,4,7-triazacyclodecane （L） has been synthesized and characterized. The metal cation is bonded with three nitrogen atoms and ...The coordination complex of Co（Ⅲ） based on a macrocyclic triamine ligand 1,4-diacetate-1,4,7-triazacyclodecane （L） has been synthesized and characterized. The metal cation is bonded with three nitrogen atoms and two oxygen atoms of L and one chloride ion to form a distorted octahedral geometry. This complex coordinated with macrocyclic ligand possesses large pore volume that will be contributed to observe high H2 adsorption. With respect to the first-principles electronic structure calculations, the feasibility to store hydrogen in the complex is explored. Indeed, the complex has shown a very high total H2 adsorption of 7.2 wt% （wt% = （weight of adsorbed H2）/（weight of host material））, with a binding energy of 0.03 eV/H2展开更多
On account of the complicated magnetic exchange interactions between lanthanide ions,binuclear lanthanide complexes have broad application prospect in the field of single-molecule magnets.Therefore,it is necessary to ...On account of the complicated magnetic exchange interactions between lanthanide ions,binuclear lanthanide complexes have broad application prospect in the field of single-molecule magnets.Therefore,it is necessary to develop reasonable bridging ligands to manipulate the directional assembly of binuclear lanthanide complexes.Herein,we selected the macrocyclic ligand L^(N_(8)O_(2))to build up two new dilanthanide complexes[Ln_(2)(LN_(8)O_(2))(OpyO)_(2)(H_(2)O)2](NO_(3))_(2)(1-Ln,Ln=Dy,Tb;LN_(8)O_(2)=hexamethyl-tetraaza-dioxe-dipyrazolacycloicosaphane-2,9,12,19-tetraene;OpyOH=2-pyridinol-1-oxide).Dynamic magnetic studies show that 1-Dy exhibits slow relaxation behavior under a 1 kOe applied field.Further fitting analysis of relaxation times gives the effective energy barrier of 38.2 cm^(−1),and reveals that the slow magnetic relaxation behavior is dominated by the Orbach and Raman processes.High-resolution luminescence emission spectrum indicates the energy gap of 36.8 cm^(−1)between the ground state and the first excited state,consistent with the magnetic measurement results.1-Tb exhibits brilliant characteristic green light emission under UV light excitation.The absolute quantum yield of 1-Tb is 44.8%,and its first-order fitted decay lifetime is 779.21μs at room temperature.This study provides the way for directional construction of high-performance molecular materials with magnetic and optical dual-function.展开更多
Three novel Zn（II） complexes,[Zn4L1Cl4]-3H2O（1）,[Zn4L2Cl4]-2DMF（2） and[Zn4L^3Cl4]H2O（3）,have been synthesized and structurally characterized.In these complexes,interesting 32-membered dodecadentate macrocyclic...Three novel Zn（II） complexes,[Zn4L1Cl4]-3H2O（1）,[Zn4L2Cl4]-2DMF（2） and[Zn4L^3Cl4]H2O（3）,have been synthesized and structurally characterized.In these complexes,interesting 32-membered dodecadentate macrocyclic ligands were generated in situ by ＇2 ＋ 2＇ type condensation reactions between a tetraamine and various dialdehydes.All the complexes are isostructurally tetranuclear Zn（Ⅱ） complexes,containing endogenous alkoxo and phenoxo bridges.Applications of the macrocyclic ligands as Zn^2＋ sensors have been investigated.Take H4L^1 for example,it exhibits a 4-fold fluorescence enhancement upon the addition of 2 equiv.of Zn^2＋ in MeOH.展开更多
Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic a...Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic acid) with 1,2-diaminopropane, (15-DTPA-1,2-pn), or 1,2-diaminocyclohexane, (15-DTPA-1,2-cy). Their lanthanide complexes [Ln(15-DTPA-1,2-pn)(H 2O)] 2 [Ln=Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H 2O)] 2 [Ln=Eu (3), Gd (4)] were also prepared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state; each metal ion is nine-coordinated in a distorted tricapped-trigonal prism. In complex 4, the coexistence of two diastereoisomeric molecules in the crystal lattice was observed.展开更多
The 6-hydroxymethyl-6'-tetrahydropyranyloxymethyl-2, 2'-bipyridine (2) was synthesized by the reaction of 6,6'-dihydroxymethyl-2, 2'-bipyridine (1) with 3, 4-dihydroxypyran (DHP). 6.Tetrahydropyranylox...The 6-hydroxymethyl-6'-tetrahydropyranyloxymethyl-2, 2'-bipyridine (2) was synthesized by the reaction of 6,6'-dihydroxymethyl-2, 2'-bipyridine (1) with 3, 4-dihydroxypyran (DHP). 6.Tetrahydropyranyloxymethyl-6'-iodomethyl-2, 2'-bipyridine (5) was obtained from mesylate and iodizating reaction of compound 2. The coupling of 2 and 5 followed by hydrolysis gave bis(6'-hydroxymethyl-2, 2'-bipyridine-6-methyl) ether (7). The macrocyclic ligand 8 was obtained by treating 7 and 6, 6'-dibromethyl-2, 2'-bipyridine. The synthetic conditions of the intermediate 2 and macocyclic ligand 8 were discussed.展开更多
A tetranuclear Mn(Ⅳ) complex \{\[L\-4Mn\-4O\-6\]\}(ClO\-4)\-4\52H\-2O (L=tacn)was synthesized from Mn(CH\-3COO)\-2\54H\-2O, tacn and NaClO\-4 and characterized by XRD. The compound crystallizes in monoclinic system, ...A tetranuclear Mn(Ⅳ) complex \{\[L\-4Mn\-4O\-6\]\}(ClO\-4)\-4\52H\-2O (L=tacn)was synthesized from Mn(CH\-3COO)\-2\54H\-2O, tacn and NaClO\-4 and characterized by XRD. The compound crystallizes in monoclinic system, space group P2\-1/n , with a =2.133 5(6) nm, b =1.138 7(3) nm, \{ c =\}\{2.178 8(6) nm\}, β =67.40(3)°, V =4.928(2) nm 3 , Z =4, R =0.062 0. Magnetic investigations reveal a weak ferromagnetic property with J =8.8 cm -1 .展开更多
基金the Robert A. Welch Foundation (A-0259) in the U.S and China Scholarship Council is gratefully acknowledged.
文摘The protonation constants of a new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, BDBPH, were determined by potentiometric measurement at 25.0 degreesC and mu = 0.100 mol.L-1 (KCl). The species distributions of the deprotonated and protonated compounds in the pH range from 2 to 12 aqueous solutions were also described.
文摘A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesized by the NaBH4 reduction of the Schiff-base obtained from the [2+2] condensation between diethylenetriamine and diformyl -p-cresol. The structure was characterized by elemental analysis, 1HNMR and FAB-MS. The synthetic method was also discussed.
文摘The hexahydro\|bromide salt of a new 24\|membered hexaaza diphenol macrocyclic ligand, （H6BDBPH）Br6·4H2O （C 26H 56N6O6Br6, Mr= 1028.23）, crystallizes in the monoclinic system, space group P21/c, with cell parameters: a=14.441（5）, b=11.482（4）, c=12.090（6）, β=96.92°, V= 1990 （1）3, Z=2, Dc=1.716 g/cm3; F（000） =1024. MoKα radiation, λ= 0.71013), R = 0.0643 and wR = 0.1356 for 3507 independent reflections with I>2σ（I）. The macrocyclic ligand adapts chair form, and the crystallographic inversion center is located in the macrocyclic cavity, and the six bromide ions and four water molecules are situated symmetrically outside the macrocyclic cavity.
文摘The intramolecular hydrogen bond self-template effect was suggested in the process of directly synthesizing the first six chiral metal-free Robson-type macrocyclic ligands. These ligands were characterized by H-1 NMR, IR, FAB-MS.
基金the Natural Science Foundation of Science and Technology Bureau of Shaanxi Province (No. 2011JM6005)the Special Foundation of Shaanxi Province Education Bureau (No. 10JK548)National Natural Science Foundation for Young Scholars (No.81001669)
文摘The coordination complex of Co（Ⅲ） based on a macrocyclic triamine ligand 1,4-diacetate-1,4,7-triazacyclodecane （L） has been synthesized and characterized. The metal cation is bonded with three nitrogen atoms and two oxygen atoms of L and one chloride ion to form a distorted octahedral geometry. This complex coordinated with macrocyclic ligand possesses large pore volume that will be contributed to observe high H2 adsorption. With respect to the first-principles electronic structure calculations, the feasibility to store hydrogen in the complex is explored. Indeed, the complex has shown a very high total H2 adsorption of 7.2 wt% （wt% = （weight of adsorbed H2）/（weight of host material））, with a binding energy of 0.03 eV/H2
基金Project supported by the National Natural Science Foundation of China(22131011,22071274,21821003)the Pearl River Talent Plan of Guangdong(2017BT01C161)。
文摘On account of the complicated magnetic exchange interactions between lanthanide ions,binuclear lanthanide complexes have broad application prospect in the field of single-molecule magnets.Therefore,it is necessary to develop reasonable bridging ligands to manipulate the directional assembly of binuclear lanthanide complexes.Herein,we selected the macrocyclic ligand L^(N_(8)O_(2))to build up two new dilanthanide complexes[Ln_(2)(LN_(8)O_(2))(OpyO)_(2)(H_(2)O)2](NO_(3))_(2)(1-Ln,Ln=Dy,Tb;LN_(8)O_(2)=hexamethyl-tetraaza-dioxe-dipyrazolacycloicosaphane-2,9,12,19-tetraene;OpyOH=2-pyridinol-1-oxide).Dynamic magnetic studies show that 1-Dy exhibits slow relaxation behavior under a 1 kOe applied field.Further fitting analysis of relaxation times gives the effective energy barrier of 38.2 cm^(−1),and reveals that the slow magnetic relaxation behavior is dominated by the Orbach and Raman processes.High-resolution luminescence emission spectrum indicates the energy gap of 36.8 cm^(−1)between the ground state and the first excited state,consistent with the magnetic measurement results.1-Tb exhibits brilliant characteristic green light emission under UV light excitation.The absolute quantum yield of 1-Tb is 44.8%,and its first-order fitted decay lifetime is 779.21μs at room temperature.This study provides the way for directional construction of high-performance molecular materials with magnetic and optical dual-function.
基金financially supported by NSFC,the Program for Professor of Special Appointment(Eastern Scholar) at Shanghai Institutions of Higher Learning,Program for New Century Excellent Talents in University(No.NCET-11-0638)Innovation Program of Shanghai Municipal Education Commission,the Fundamental Research Funds for the Central Universities(No.WK1013002)+1 种基金SRFDP(No.20100074110015)S.W.Ng is grateful for support by the University of Malaya(No.UM.C/625/1/H1R/033/10)
文摘Three novel Zn（II） complexes,[Zn4L1Cl4]-3H2O（1）,[Zn4L2Cl4]-2DMF（2） and[Zn4L^3Cl4]H2O（3）,have been synthesized and structurally characterized.In these complexes,interesting 32-membered dodecadentate macrocyclic ligands were generated in situ by ＇2 ＋ 2＇ type condensation reactions between a tetraamine and various dialdehydes.All the complexes are isostructurally tetranuclear Zn（Ⅱ） complexes,containing endogenous alkoxo and phenoxo bridges.Applications of the macrocyclic ligands as Zn^2＋ sensors have been investigated.Take H4L^1 for example,it exhibits a 4-fold fluorescence enhancement upon the addition of 2 equiv.of Zn^2＋ in MeOH.
基金theNationalNaturalScienceFoundationofChina (No .2 0 0 72 0 2 7)
文摘Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic acid) with 1,2-diaminopropane, (15-DTPA-1,2-pn), or 1,2-diaminocyclohexane, (15-DTPA-1,2-cy). Their lanthanide complexes [Ln(15-DTPA-1,2-pn)(H 2O)] 2 [Ln=Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H 2O)] 2 [Ln=Eu (3), Gd (4)] were also prepared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state; each metal ion is nine-coordinated in a distorted tricapped-trigonal prism. In complex 4, the coexistence of two diastereoisomeric molecules in the crystal lattice was observed.
文摘The 6-hydroxymethyl-6'-tetrahydropyranyloxymethyl-2, 2'-bipyridine (2) was synthesized by the reaction of 6,6'-dihydroxymethyl-2, 2'-bipyridine (1) with 3, 4-dihydroxypyran (DHP). 6.Tetrahydropyranyloxymethyl-6'-iodomethyl-2, 2'-bipyridine (5) was obtained from mesylate and iodizating reaction of compound 2. The coupling of 2 and 5 followed by hydrolysis gave bis(6'-hydroxymethyl-2, 2'-bipyridine-6-methyl) ether (7). The macrocyclic ligand 8 was obtained by treating 7 and 6, 6'-dibromethyl-2, 2'-bipyridine. The synthetic conditions of the intermediate 2 and macocyclic ligand 8 were discussed.
文摘A tetranuclear Mn(Ⅳ) complex \{\[L\-4Mn\-4O\-6\]\}(ClO\-4)\-4\52H\-2O (L=tacn)was synthesized from Mn(CH\-3COO)\-2\54H\-2O, tacn and NaClO\-4 and characterized by XRD. The compound crystallizes in monoclinic system, space group P2\-1/n , with a =2.133 5(6) nm, b =1.138 7(3) nm, \{ c =\}\{2.178 8(6) nm\}, β =67.40(3)°, V =4.928(2) nm 3 , Z =4, R =0.062 0. Magnetic investigations reveal a weak ferromagnetic property with J =8.8 cm -1 .
