以2,5-二羟基-1,4-对苯二甲酸为配体的稀土配合物的合成、晶体结构和磁学性质
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摘要
以2,5-二羟基-1,4-对苯二甲酸(H_4DHBDC)和Ln(NO_3)_3·6H_2O(Ln=Dy,Tb)为原料,通过溶剂热反应得到了两个新的配合物{[Ln_2(H_2-DHBDC)_3(DMF)_4]}_n(Ln=Dy(1),Tb(2))。通过单晶X射线衍射、红外光谱、热重分析和粉末X射线衍射对配合物进行了表征。结果表明,配合物1和2是完全同构的化合物,结晶于三斜空间群P-1中。配合物的次级结构单元中含有2个中心离子、6个去质子的配体和4个N,N-二甲基甲酰胺分子,并进一步通过周围的羧酸根基团以两种不同的桥连模式,形成了三维框架结构。磁性测试结果表明,配合物1在80 kA/m外加直流场条件下具有慢磁弛豫性质。
Two new types of complexes, {[Ln_2(H_2-DHBDC)_3(DMF)_4]}_n(Ln=Dy(1),Tb(2)) were obtained by solvothermal reaction using 2,5-dihydroxy-1,4-terephthalic acid(H_4DHBDC) and Ln(NO_3)_3·6 H_2O(Ln=Dy, Tb) as raw materials. The complexes were characterized by single crystal X-ray diffraction method, Fourier transform infrared spectroscopy, thermogravimetric analysis and powder X-ray diffraction method. The results show that the two complexes were completely isomorphous compound and crystallized in the triclinic system, space group P-1. The secondary building unit of the two compounds consist of two metal ions, three deprotonated ligands and four N, N-Dimethylformamide molecules. And three dimensional frame structure was further formed through the surrounding carboxylic acid groups with two different carboxylic bridging modes. Studies on the magnetic properties show that the complex exhibited slow magnetic relaxation behaviors.
Two new types of complexes, {[Ln_2(H_2-DHBDC)_3(DMF)_4]}_n(Ln=Dy(1),Tb(2)) were obtained by solvothermal reaction using 2,5-dihydroxy-1,4-terephthalic acid(H_4DHBDC) and Ln(NO_3)_3·6 H_2O(Ln=Dy, Tb) as raw materials. The complexes were characterized by single crystal X-ray diffraction method, Fourier transform infrared spectroscopy, thermogravimetric analysis and powder X-ray diffraction method. The results show that the two complexes were completely isomorphous compound and crystallized in the triclinic system, space group P-1. The secondary building unit of the two compounds consist of two metal ions, three deprotonated ligands and four N, N-Dimethylformamide molecules. And three dimensional frame structure was further formed through the surrounding carboxylic acid groups with two different carboxylic bridging modes. Studies on the magnetic properties show that the complex exhibited slow magnetic relaxation behaviors.
引文
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[4] Cosquer G, Shen Y, Almeida M, et al. Conducting single-molecule magnet materials[J]. Dalton Transactions, 2018,47(23):7616-7627.
[5] She S, Gong L, Wang B, et al. Slow magnetic relaxation in a two-dimensional dysprosium(Ⅲ) coordination polymer[J]. Inorganic Chemistry Communications, 2016, 70:18-21.
[6] Guo F, Day B M, Chen Y, et al. A dysprosium metallocene single-molecule magnet functioning at the axial limit[J]. Angew Chem Int Ed, 2017, 129(38):11445-11449.
[7] Donati F, Rusponi S, Stepanow S, et al. Magnetic remanence in single atoms[J]. Science, 2016, 352(6283):318-321.
[8] Huang G, Fernandez-Garcia G, Bernot K. Magnetic slow relaxation in a metal-organic framework made of chains of ferromagnetically coupled single-molecule magnets[J]. Chemistry-A European Journal, 2018, 24(27): 6983-6991.
[9] She S, Liu B, Yang Y, et al. Slow magnetic relaxation in a carboxylate-bridged one dimensional dysprosium complex[J].Inorganic Chemistry Communications, 2015, 61:132-135.
[10] Kilpatrick A, Guo F S, Day B M, et al. Single-molecule magnet properties of a monometallic dysprosium pentalene complex[J]. Chemical Communications, 2018, 54(51):7085-7088.
[11] Ungur L, Chibotaru L F. Strategies toward high-temperature lanthanide-based single-molecule magnets[J]. Inorgnic Chemistry,2016, 55:10043-10056.
[12] Ren Wen, Zheng Limin. Single-molecule magnet of rare earth[J]. Journal of Chemistry, 2015,73(11):1091-1113(in Chinese). 任旻,郑丽敏.稀土单分子磁体[J]. 化学学报,2015,73(11):1091-1113.
[13] Zhang Y, Wu L, Guo X, et al. Molecular dynamics simulation of electrical resistivity in sintering process of nanoparticle silver inks[J]. Computational Materials Science, 2016, 125:105-109.
[14] Zhang N,Liu H X, Zhou Z ,et al. Adsorptive removal of boron by zeolitic imidazolate framework: kinetics, isotherms, thermodynamics, mechanism and recycling[J]. Separation and Purification Technology,2017,187:67-75.
[15] Qiao S, Zhang J, Zhang S, et al. Field-induced single-molecule magnet (SMM) behavior of dinuclear Dy(Ⅲ) system[J]. Inorganica Chimica Acta, 2018, 6(2):45-53.
[16] She S, Su G, Wang B, et al. Two dysprosium(Ⅲ) based single-molecule magnets derived from phen (phen = 1,10-phenantroline) ligand and different anion ions act as bridging groups[J]. Berichte Der Deutschen Chemischen Gesellschaft, 2017, 2017(18):2406-2412.
[17] Feng M, Tong M L. Single ion magnets from 3d to 5f: developments and strategies[J] .Chemistry-A European Journal,2018,24(30):7574-7590.
[18] Aldoshin S M, Korchagin D V, Palii A V, et al. Some new trends in the design of single molecule magnets[J]. Pure and Applied Chemistry,2017,89(8):116-118.
[19] Zhang X M, Li P, Gao W, et al. Construction of three lanthanide metal-organic frameworks: Synthesis, structure, magnetic properties and highly selective sensing of metal ions[J] . Journal of Solid State Chemistry,2016,244:6-11.
[20] Ding Y S, Chilton N F, Winpenny R E, et al. On approaching the limit of molecular magnetic anisotropy: a near-perfect pentagonal bipyramidal dysprosium(Ⅲ) single-molecule magnet[J]. Angewandte Chemie, 2016, 55(52):16071-16074.
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[22] Wang Y L, Jiang Y L, Liu Q Y, et al. A series of three-dimensional lanthanide(Ⅲ) coordination polymers of 2,5-dihydroxy-1,4-benzene dicarboxylic acid based on dinuclear lanthanide units[J]. CrystEngComm, 2011, 13(15):4981-4987.
[23] Yang Yan, Lei Quan, Su Gangping, et al. Synthesis and magnetic properties of two one-dimensioal lanthanide complexes bridged by carboxylate ions[J]. Journal of Synthetic Crystals, 2017, 46(7):1348-1354(in Chinese).杨燕, 雷全, 苏港平,等. 羧酸根桥连稀土一维链配合物的制备及磁性能研究[J]. 人工晶体学报, 2017, 46(7):1348-1354.
[24] Ge J Y, Wang H Y, Su J, et al. Modulating the magnetic interaction in new triple-decker dysprosium(Ⅲ) single-molecule magnets[J]. Inorganic Chemistry, 2018, 57(3):1408-1416.