手性镝(III)-酒石酸配合物的合成、单晶转换及热稳定性研究

摘要/Abstract

摘要： 以2,3-二乙酰对甲苯-D-酒石酸(D-H₂DTTA)为原料,与金属Dy(III)盐反应,经过单晶-单晶转换,得到一种新的酒石酸(H₂tar)配合物[Dy(Htar)₃(H₂O)₃]_n(1),对该配合物用元素分析、红外光谱、X-射线单晶衍射、粉末衍射以及差热-热重等进行了表征。晶体结构分析表明,配合物1属三方晶系,R3空间群,晶胞参数为a=b=2.723 16(14) nm,c=0.762 75(6) nm,α=β=90.00°,γ=120.00°,V=4.898 5 (6) nm³,Z=3, 剑桥晶体数据库(Cambridge Crystallographic Data Centre, CCDC)编号为1498504。配合物中的金属Dy³⁺分别与三个酒石酸离子配体Htar^-上的六个氧原子和三个配位水分子上的三个氧原子配位,形成九配位三帽三棱柱构型。配合物1在c方向上通过O1和O5原子连接成一维链状结构,相邻Dy³⁺之间的距离为0.762 8(1) nm。配合物1是由[Dy(HDTTA)₃(CH₃OH)₃]_n经单晶-单晶转换过程得到,其转换过程包括酯基水解及水分子取代两类反应。配合物1具有一定的热稳定性,45~166 ℃失去配位水分子,高于166 ℃配合物骨架坍塌。

关键词: 酒石酸, Dy(III)配合物, 单晶-单晶转换, 热稳定性

Abstract: The new complex [Dy(Htar)₃(H₂O)₃]_n(1) was synthesized by the single crystal to single crystal transformation method using(+)-di-p-toluoyl-D-tartaric acid (D-H₂DTTA) as raw material and reaction with mentalic Dy(III) salt. The complex was characterized by elemental analysis, IR spectroscopy, single crystal X-ray diffraction, powder X-ray diffraction analysis and thermogravimetric analysis and differential thermal analysis(TGA-DTA). The results of X-ray crystallographic analysis indicate that complex 1 belongs to trigonal system, space group R3 with a=b=2.723 16(14) nm, c=0.762 75(6) nm, α=β=90.00°, γ=120.00°, V=4.898 5 (6) nm³, Z=3, and Cambridge Crystallographic Data Centre (CCDC) number is 1498504. Each Dy³⁺ is surrounded by six O atoms from three Htar^- ligands and three O atoms from three coordinated water molecules, forming a tricapped trigonal prism geometry with nine coordination property. Complex 1 exhibits an infinite one dimensional chain structure connected by O1 and O5 along c axis, with the Dy…Dy distance of 0.762 8(1) nm. Complex 1 was obtained through single crystal to single crystal transformation process from [Dy(HDTTA)₃(CH₃OH)₃]_n, which includes ester hydrolysis and water molecules substitution two reactions. Complex 1 has a certain thermal stability. After taking off the coordinated water molecules in the range of 45~166 ℃, the skeleton of 1 begins to collapse with increasing temperature above 166 ℃.

Key words: tartaric acid, Dy(III) complex, single crystal to single crystal transformation, thermal stability

中图分类号:

O614

李丽, 郑剑锋, 赵明霞, 冯思思. 手性镝(III)-酒石酸配合物的合成、单晶转换及热稳定性研究[J]. 人工晶体学报, 2021, 50(1): 106-112.

LI Li, ZHENG Jianfeng, ZHAO Mingxia, FENG Sisi. Synthesis, Single Crystal Transformation and Thermal Stability of Chiral Dysprosium (III)-Tartaric Acid Complex[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(1): 106-112.

参考文献

[1] SUN X L, SONG W C, ZANG S Q, et al. Hierarchical assembly of a homochiral triple concentric helical system in a novel 3D supramolecular metal-organic framework: synthesis, crystal structure, and SHG properties[J]. Chemical Communications (Cambridge,England), 2012, 48(15): 2113-2115.
[2] WANG Y T, TANG G M, WAN W Z, et al. New homochiral ferroelectric supramolecular networks of complexes constructed by chiral S-naproxen ligand[J]. Cryst Eng Comm, 2012, 14(10): 3802-3812.
[3] HE J H, ZHANG G J, XIAO D R, et al. From racemic compound to spontaneous resolution: a series of homochiral lanthanide coordination polymers constructed from presynthesized [Sb₂(tart)₂]₂- metalloligands[J]. Journal of Molecular Structure, 2012, 1018: 131-136.
[4] TRAIN C, GRUSELLEC M, VERDAGURE M. The fruitful introduction of chirality and control of absolute configurations in molecular magnets[J]. Chemical Society Reviews, 2011, 40(6): 3297-3312.
[5] WEN H R, TANG Y Z, LIU C M, et al. One-dimensional homochiral cyano-bridged heterometallic chain coordination polymers with metamagnetic or ferroelectric properties[J]. Inorganic Chemistry, 2009, 48(21): 10177-10185.
[6] JIANG Z G, LU Y K, CHENG J W, et al. Two types of rare earth-organic frameworks constructed by racemic tartaric acid[J]. Journal of Solid State Chemistry, 2012, 185: 253-263.
[7] WU C D, LU C Z, LU S F, et al. Synthesis, structures and properties of a series of novel left- and right-handed metal coordination double helicates with chiral channels[J]. Dalton Transactions, 2003, 3(16): 3192-3198.
[8] THUSHARI S, CHA J A K, SUNG H H Y, et al. Microporous chiral metal coordination polymers: hydrothermal synthesis, channel engineering and stability of lanthanide tartrates[J]. Chemical Communications (Cambridge,England), 2005(44): 5515-5517.
[9] ATHAR M, LI G H, SHI Z, et al. Hydrothermal synthesis and structural characterization of a family of lanthanide tartrates: [Ln₂(C₄H₄O₆)₃(H₂O)₃]·1.5H₂O (Ln = La, Ce, Pr, Nd, Sm) [J]. Solid State Sciences, 2008, 10(12): 1853-1859.
[10] WANG Y, LIU G X, CHEN Y C, et al. Two novel lanthanum-tartrate complexes with distinctive new topologies: hydrothermal synthesis and crystal structures[J]. Inorganica Chimica Acta, 2010, 363(11): 2668-2672.
[11] CHAUDHARY A, MOHAMMAD A, MOBIN S M. Recent advances in single-crystal-tosingle-crystal transformation at the discrete molecular level[J]. Crystal Growth & Design, 2017, 17(5): 2893-2910.
[12] ROSI N L, EDDAOUDI M, KIM J, et al. Infinite secondary building units and forbidden catenation in metal-organic frameworks[J]. Angewandte Chemie (International Ed.in English), 2002, 41(2): 284-287.
[13] HO T Y, HUANG S M, WU J Y, et al. Direct guest exchange induced single-crystal to single-crystal transformation accompanying irreversible crystal expansion in soft porous coordination polymers[J]. Crystal Growth & Design, 2015, 15(9): 4266-4271.
[14] ZHANG X, VIERU V, FENG X, et al. Influence of guest exchange on the magnetization dynamics of dilanthanide single-molecule-magnet nodes within a metal-organic framework[J]. Angewandte Chemie (International Ed in English), 2015, 54(34): 9861-9865.
[15] KYPRIANIDOU E J, LAZARIDES T, KAZIANNIS S, et al. Single crystal coordinating solvent exchange as a general method for the enhancement of the photoluminescence properties of lanthanide MOFs[J]. Journal of Materials Chemistry A, 2014,2(15): 5258.
[16] LIU Z Y, YANG E C, LI L L, et al. A reversible SCSC transformation from a blue metamagnetic framework to a pink antiferromagnetic ordering layer exhibiting concomitant solvatochromic and solvatomagnetic effects[J]. Dalton Transactions, 2012, 41(22): 6827-6832.
[17] HAN M R, ZHANG H T, WANG J N, et al. Three chiral one-dimensional lanthanide-ditoluoyl-tartrate bifunctional polymers exhibiting, luminescence and magnetic behaviors[J]. RSC Advances, 2019, 9(55): 32288-32295.
[18] BRUKER. APEX2 and SAINT. Bruker AXS Inc[M]. Madison, Wisconsin, USA. 2000.
[19] SHELDRICK G M. A short history of SHELX[J]. Acta Cryst, 2008, A64: 112-122.
[20] SHELDRICK G M. SHELXT-Integrated space-group and crystal-structure determination[J]. Acta Crystallogr A Found Adv, 2015, 71(pt 1): 3-8.
[21] SPEK A L. Single-crystal structure validation with the program PLATON[J]. Journal of Applied Crystallography, 2003, 36(1): 7-13.
[22] ZHAO N, Sun F X, He H M, et al. Solvent-induced single crystal to single crystal transformation and complete metal exchange of a pyrene-based metal-organic framework[J]. Crystal Growth & Design, 2014, 14(4):1738-1743.
[23] SU F, Lu L P, Feng S S, et al. Self-assembly and magnetic properties of Ni(ii)/Co(ii) coordination polymers based on 1,4-bis(imidazol-1-yl)benzene and varying biphenyltetracarboxylates[J].CrystEngComm, 2014, 16(34): 7990-7999.
[24] MA X L, Wang Z X, He X, et al. 2D double-layered dibenzoyl-tartrate chiral coordination polymer containing [Mn₄L₂(bpp)₄] tetrahedral cage[J]. Inorganic Chemistry Communications, 2018, 92: 131-135.
[25] GAO Q, Wang X Q, Jacobson A J. Homochiral frameworks formed by reactions of lanthanide ions with a chiral antimony tartrate secondary building unit[J]. Inorganic Chemistry, 2011, 50(18): 9073-9082.
[26] SUN J W, Li S J, Yan P F, et al. In situ recrystallization of lanthanide coordination polymers: from 1D ladder chains to 1D linear chains[J]. CrystEngComm, 2016, 18(17): 3079-3085.
[27] LI Y X, Li S J, Yan P F, et al. Luminescence-colour-changing sensing of Mn²⁺and Ag⁺ ions based on a white-light-emitting lanthanide coordination polymer[J]. Chemical Communications (Cambridge, England), 2017, 53(26): 5067-5070.