联吡啶四唑铜(Ⅱ)配合物的原位合成、结构及性质
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摘要
采用水热合成法,通过配体5,5'-二氰基-3,3'-联吡啶和叠氮化钠在路易斯酸CuSO_4的作用下,得到了一种新型的金属有机铜四唑配合物。X射线单晶衍射结构表明,该化合物属于四方晶系,P4/ncc空间群。它是由吡啶环中的N原子连接形成的无限延展的二维网状结构;硫酸根阴离子位于中心金属周围,且高度无序的硫酸根离子很有可能在低温下变成有序,从而引起结构相变。该化合物的堆积图形状类似一个蝴蝶发卡。其高含氮结构可作为潜在的高含能材料。
Hydrothermal reaction of 5,5'-dicyano-3,3'-bipyridyl ligands and sodium azide in the presence of the Lewis acid CuSO_4 in water and ethanol provided a novel metal organic tetrazole complex. X-ray single crystal diffraction analysis shows that this complex belongs to a tetragonal system with P4/ncc space group.This complex displays an interesting infinite two-dimensional( 2 D) network structure bridge linked by the pyridyl N atoms. The highly disordered sulfate around the central metals are likely to become ordered at low temperatures,leading to structural phase changes. The packing diagram of the crystal structure shows a butterfly hairpin shape. The highly nitrogenated structure allows this complex to be a potential high-energy material.
Hydrothermal reaction of 5,5'-dicyano-3,3'-bipyridyl ligands and sodium azide in the presence of the Lewis acid CuSO_4 in water and ethanol provided a novel metal organic tetrazole complex. X-ray single crystal diffraction analysis shows that this complex belongs to a tetragonal system with P4/ncc space group.This complex displays an interesting infinite two-dimensional( 2 D) network structure bridge linked by the pyridyl N atoms. The highly disordered sulfate around the central metals are likely to become ordered at low temperatures,leading to structural phase changes. The packing diagram of the crystal structure shows a butterfly hairpin shape. The highly nitrogenated structure allows this complex to be a potential high-energy material.
引文
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[16]Tan Y H,Xiong J B,Gao J X,et al.Solvothermal Synthesis,Structure,and Fluorescence Properties of Three d10Polymers Assembled from Semi-Rigid V-Shaped Aza-Bridged Multicarboxylate[J].RSC Adv,2015,5:30216-30221.
[17]GUAN Lei,GAO Wei,ZHANG Zukang,et al.Synthesis,Crystal Structures and Luminescent Properties of Two Nickel Mononuclear Complexes Containing N-Donor Ligands[J].Chinese J Inorg Chem,2014,30(5):1187-1194(in Chinese).关磊,高威,张祖康.两个单核镍含氮配体配合物的合成、晶体结构及荧光性质[J].无机化学学报,2014,30(5):1187-1194.
[2]DAI Lingling,CUI Shengfeng,Guri L V Damu,et al.Recent Advances in the Synthesis and Application of Tetrazoles[J].Chinese J Org Chem,2013,33(2):224-244(in Chinese).代玲玲,崔圣峰,Guri L V Damu,等.四唑类化合物的合成及应用研究新进展[J].有机化学,2013,33(2):224-244.
[3]Zhang H Z,Zhou C H,Geng R X,et al.Recent Advances in Syntheses of Oxazole Compounds[J].Chinese J Org Chem,2011,31(12):1963-1976.
[4]Gao J X,Xiong J B,Xu Q,et al.Supramolecular Interactions Induced Chirality Transmission,Second Harmonic Generation Responses,and Photoluminescent Property of a Pair of Enantiomers from in Situ[2+3]Cycloaddition Synthesis[J].Cryst Growth Des,2016,16(3):1559-1564.
[5]Tan Y H,Wu J J,Yang L F,et al.Anion and p H Induced Spontaneous Resolution ofΔ-andΛ-[M(H2Biim)3]SO4(M=Ru2+,Co2+,Ni2+,Mn2+,Fe2+,and Zn2+)Enantiomers[J].Cryst Eng Comm,2012,14:8117-8123.
[6]Tang Y Z,Xiong J B,Gao J X,et al.Spontaneous Resolution,Asymmetric Catalysis,and Fluorescence Properties ofΔ-andΛ-[Cu(Tzmp)]nEnantiomers from in Situ[2+3]Cycloaddition Synthesis[J].Inorg Chem,2015,54(11):5462-5466.
[7]Himo F,Demko Z P,Sharpless K B,et al.Mechanisms of Tetrazole Formation by Addition of Azide to Nitriles[J].J Am Chem Soc,2002,124(41):12210-12216.
[8]Demko Z P,Sharpless K B.Preparation of 5-Substituted 1H-tetrazoles from Nitriles in Water[J].Org Chem,2001,66(24):7945-7950.
[9]Sheldrick G M.SHELXS-97,Program for X-ray Crystal Structure Determination[CP].University of G9ttingen,Germany,1997.
[10]Sheldrick G M.SHELXS-97,Program for Crystal Structure Solution[CP].University of G9ttingen,Germany,1997.
[11]TAN Yuhui,XIONG Jianbo,HUANG Jun,et al.A Family of Tetrazole Compounds Formed Through in situ[2+3]Tetrazole Ligand Synthesis,Structures and Fluorescent Properties[J].Chinese J Inorg Chem,2014,30(7):1621-1628(in Chinese).谭育慧,熊剑波,黄珺.原位[2+3]环合成法制备四唑化合物、结构及荧光性质[J].无机化学学报,2014,30(7):1621-1628.
[12]SU Chengyong,PAN Mei.Chemical Basis and Progress of Coordination Supramolecular Structure[M].Beijing:Science Press,2010,2:64-65(in Chinese).苏成勇,潘梅.配位超分子结构化学基础与进展[M].北京:科学出版社,2010,2:64-65.
[13]Qin J,Lei N,Ding H,et al.Synthesis and Reactivity in Inorganic,Metal-Organtic,and Nano-Metal[J].Chemistry,2016,46(7):968-974.
[14]TAN Yuhui,GU Zhifeng,LIU Yi,et al.Synthesis,Structure and Fluorescence Properties of Manganese(Ⅱ)Complex Based on 3-Carboxyl-1,2,4-triazole[J].Chinese J Appl Chem,2017,34(3):354-360(in Chinese).谭育慧,古志峰,刘艺.3-羧基-1,2,4-三氮唑MnⅡ配合物的合成、结构及荧光性质[J].应用化学,2017,34(3):354-360.
[15]XU Qing,GAO Jixing,GU Zhifeng,et al.Syntheses,Structures and Fluorescence Properties of ZnⅡComplex with 2-(2-Pyridyl)-4-hydroxy Quinazoline[J].Nonferrous Met Sci Eng,2015,6(6):144-148(in Chinese).徐庆,高继兴,古志峰.2-(2-吡啶基)-4-羟基喹唑啉锌配合物的合成、结构及荧光性质[J].有色金属科学与工程,2015,6(6):144-148.
[16]Tan Y H,Xiong J B,Gao J X,et al.Solvothermal Synthesis,Structure,and Fluorescence Properties of Three d10Polymers Assembled from Semi-Rigid V-Shaped Aza-Bridged Multicarboxylate[J].RSC Adv,2015,5:30216-30221.
[17]GUAN Lei,GAO Wei,ZHANG Zukang,et al.Synthesis,Crystal Structures and Luminescent Properties of Two Nickel Mononuclear Complexes Containing N-Donor Ligands[J].Chinese J Inorg Chem,2014,30(5):1187-1194(in Chinese).关磊,高威,张祖康.两个单核镍含氮配体配合物的合成、晶体结构及荧光性质[J].无机化学学报,2014,30(5):1187-1194.