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Journal of Rare Earths 2024年第7期42卷 1298-1303,I0004页

作者： Pei-Yu Liao Yu-Quan Qi Zhen Li Jian-Hua Jia Ming-Liang Tong Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education School of ChemistrySun Yat-Sen UniversityGuangzhou510006China

On account of the complicated magnetic exchange interactions between lanthanide ions,binuclear lanthanide complexes have broad application prospect in the field of single-molecule ***,it is necessary to develop reasonable bridging ligands to manipulate the directional assembly of binuclear lanthanide ***,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 *** 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 ***-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 *** absolute quantum yield of 1-Tb is 44.8%,and its first-order fitted decay lifetime is 779.21μs at room *** study provides the way for directional construction of high-performance molecular materials with magnetic and optical dual-function.

关键词： Dilanthanide complexes Single-molecule magnets macrocyclic ligand Photoluminescence behavior Rare earths

The Crystal and Molecular Structure of a New macrocyclic ligand, (H_6BDBPH)Br_6·4H_2O

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Chinese Journal of Structural Chemistry 2000年第5期19卷 334-337页

作者： SHANGGUAN Guo\|Qiang (Department of Chemistry, Jining Medical College, Jining 272013) [WT4”BZ]Arthur E. Martell Zhongren Zhang Joseph Reibenspies (Department of Chemistry, Texas A&M University, College Station, Texas 77842, USA) 济宁医学院山东济宁 2 72 0 1 3 Texas A&M University 美国 Texas 77842

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.

关键词： macrocyclic ligand synthesis crystal structure

Synthesis, Characterization and Antitumor Activities of Co, Ni, Cu, Zn Complexes with 1,4,7,10-tetrakis(4-nitrobenzyl)-1,4,7,10 tetraazacyclododecane macrocyclic ligand

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Chinese Journal of Structural Chemistry 2000年第1期19卷 39-47页

作者： KONG De\|Yuan a* \ XIE Yu\|Li a\ XIE Yu\|Yuan a\ HUANG Xiao\|Ying ba (Shanghai Institute of Materia Medica, the Chinese Academy of Sciences, Taiyuan Road 294, Shanghai, 200031, P. R. China) b (Department of Chemistry, Rugters University, New Jer 中科院上海药物所上海 2 0 0 0 31 Rugters University 美国 New Jersey 08102

New tetraazamacrocyclic ligand with 1,4,7,10 tetrakis(4 nitrobenzyl) pendent groups (C 36 H 40 N 8O 8, M r =712.76) crystallized in the monoclinic system, P2 1/n space group with unit cell parameters: a=7.834(2), b=22.902(6), c=10\^147(3), β=106.53(2)°, V=1745(1) 3, Z=2, D c =1.356 g/cm 3, λ (Mo Kα )=0.71069; μ =0.92cm -1 , F(000)=752, T =296K. The final R and R w values are 0\^065 and 0.066, respectively. The Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ), Zn(Ⅱ) complexes with this new ligand have been synthesized and characterized by elemental analyses, IR, UV, ESI MS and molar conductance. The macrocyclic ligand molecular structure is centrosymmetrical. All complexes are in accordance with the general formula: M(L)(NO 3) 2·nH 2O (M=Co, Ni, Cu, n=2; M=Zn, n=4; L=C 36 H 40 \|N 8O 8). The central metal ions coordinate to four nitrogen atoms of azamacrocycle and two oxygen atoms of one nitrate ion. Preliminary pharmacological tests against P 388 and A 549 tumor cell lines showed that all these complexes had considerable activities in vitro.

关键词： synthesis macrocyclic ligand antitumor activity crystal structure

Synthesis of a novel macrocyclic ligand containing bipyridine units

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Chinese Journal of Chemistry 2000年第3期18卷 384-387页

作者：何永炳 LEHN Jean-Marie Department of Chemistry Wuhan University Wuhan Hubei 430072 China

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'-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.

关键词： azacrown ether bipyridine derivative macrocyclic ligand

The Synthesis of a New macrocyclic Dinucleating ligand,3,6,9,17,20,23-Hexaaza-29,30-Dihydroxy-13,27-Dimethyl-Tricyclo[23,3,1,1^(11,15)]Triaconta-1(28),11,13, 15(30),25,26-Hexaene

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Chinese Chemical Letters 2000年第7期11卷 573-576页

作者： Guo Qiang SHANGGUAN Arthur E. MARTELL Zhong Ren ZHANG (Department of Chemistry, Jining Medical College, Jining 272013Department of Chemistry, Texas A&M University, College Station, Texas 77842 USA) Jining Med Coll Dept Chem Jining 272013 Peoples R China Texas A&M Univ Dept Chem College Stn TX 77842 USA

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.

关键词： macrocyclic ligand synthesis

The Determination of the Protonation Constants of A New macrocyclic Dinucleating ligand, BDBPH

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Chinese Chemical Letters 2001年第2期12卷 171-174页

作者： Guo Qiang SHANGGUAN Ning WANG Hong En WANG Arthur EMARTELL Department of Chemistry Jining Medical CollegeJining 272013 Department of Chemistry Texas A&M UniversityCollege StationTexas 77842

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.

关键词： Protonation constant potentiometric measurement macrocyclic ligand

Syntheses and Crystal Structures of Lanthanide Complexes of New 15-Membered macrocyclic ligands with Three Pendant Acetato Groups

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Chinese Journal of Chemistry 2003年第9期21卷 1213-1218页

作者：姚英明沈琪黄永德 Department of Chemistry and Chemical Engineering Suzhou University Suzhou Jiangsu 215006 China Department of Chemistry The University of Hong Kong Pokfulam Road Hong Kong China

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.

关键词： macrocyclic ligand lanthanide complex synthesis crystal structure

Manganese catalyzed asymmetric transfer hydrogenation of ketones

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Chinese Chemical Letters 2021年第4期32卷 1415-1418页

作者： Guang-Ya Zhang Sun-Hong Ruan Yan-Yun Li Jing-Xing Gao Department of Chemistry College of Chemistry and Chemical EngineeringNational Engineering Laboratory for Green Chemical Production of Alcohols-Ethers-EstersXiamen UniversityXiamen 361005China

The asymmetric transfer hydrogenation(ATH)of a wide range of ketones catalyzed by manganese complex as well as chiral P_(x)N_(y)-type ligand under mild conditions was *** 2-propanol as hydrogen source,various ketones could be enantioselectively hydrogenated by combining cheap,readily available[MnBr(CO)_(5)]with chiral,22-membered macrocyclic ligand(R,R,R',R')-CyP_(2)N_(4)(L_(5))with 2 mol%of catalyst loading,affording highly valuable chiral alcohols with up to 95%ee.

关键词： Asymmetric catalysis Manganese Ketones macrocyclic ligand Asymmetric transfer hydrogenation

Synthesis of a Hexagonal Molecular Nickel-wheel

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Chinese Journal of Structural Chemistry 2015年第11期34卷 1689-1696页

作者：谢兴昆张晓峰刘海雄王阳陈昌能黄德光 College of Chemistry Fuzhou University State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of Sciences

The macrocyclic ligand c-H2pyN2-O3ane （2） was readily prepared in a diluted condition in THF. The mixture of 2 and Ni（OTf）2 in DMF using Et4NOH as the base source gave a mononuclear square planar complex （Et4N）[Ni（OH）（c-pyNE-O3ane）] （3）. Addition of Fe（OTf）2 into the solution of 3 in DMF instantly generated a hexagonal molecular nickel-wheel 4 in 72% yield. Both 3 and 4 were characterized by X-ray crystallography on a MoKa radiation diffractometer （λ= 0.71073 A）： the crystal of 3 was grown in space group P212121 with a = 12.079（5）, b=15.099（6）, c = 17.299（8） A, V = 3160（2） A3, Z = 4, Dc = 1.369 g/cm3, F（000） = 1384, C33H44N4NiO6, Mr = 651.43, μ= 0.665 cm-1, R = 0.0353, wR = 0.0668 for 4548 observed reflections with I〉 2σ（I）; 4 is in space group P21/n with a = 17.7416（17）, b = 17.5490（17）, c = 29.036（3）A,β = 106.195（2）°, V= 8681.5（14） As, Z = 2, Dc = 1.352 g/cm3, F（000） = 3704, C170H190N22Ni6O40, Mr = 3533.70,μ = 719 cm-1, R = 0.0841 and wR = 0.2339 for 9371 observed reflections with I〉 2σ（I）.

关键词： macrocyclic ligand hydroxide hexagonal nickel-wheel