一维链状Pb(Ⅱ)配位聚合物的制备、晶体结构及荧光性质
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摘要
以硝酸铅、对苯二甲酸、2,2’-联吡啶为原料,利用水热合成法制备了一种新型一维链Pb(Ⅱ)配位聚合物[Pb(TP)(2,2’-bipy)]_n(TP=对苯二甲酸,2,2’-bipy=2,2’-联吡啶)。通过X射线单晶衍射、元素分析、红外光谱、荧光分析等技术对目标配合物进行了结构及性质表征。结构分析表明,目标配合物属于三斜晶系,空间群为P-1,晶胞参数a=0. 94440 nm,b=0. 95273nm,c=1. 04054 nm,α=113. 179(3)°,β=80. 0140(3)°,γ=100. 774(3)°,V=0. 80677 nm~3,Z=2。对苯二甲酸配体上的两个羧基利用螯合配位模式分别连接两个Pb离子形成Z字形一维链状结构,一维链节点上的2,2’-联吡啶中两个吡啶环通过π-π堆积相互作用形成二维及三维超分子结构。荧光分析表明,配合物的荧光主要表现为配体的π~*→π跃迁。
One chain-like coordination polymer [Pb( TP)( 2,2'-bipy) ]n( TP = terephthalic acid,2,2 '-bipy = 2,2'-bipyridine) was synthesized under of hydrothermal reaction based on lead nitrate,terephthalic acid and 2,2 '-bipyridine. The structure and properties of the target complex were characterized by X-ray single crystal diffraction,EA,IR and fluorescence analysis. The X-ray crystallographic analysis reveals that complex 1 crystallizes in the triclinic system,space group P-1. The crystal cell parameters are a = 0. 9444 nm,b = 0. 95273 nm,c =1. 04054 nm,α = 113. 179( 3) °,β = 80. 0140( 3) °,γ = 100. 774( 3) °,V = 0. 80677 nm~3,Z = 2,respectively.Both the two carboxylate groups of TP are adopt chelated coordination mode linking two Pb2 +ions forming a 1 D zigzag-like chain along a axis. The π-π packing interactions between the 2,2 '-bipy ligands from the adjacent 1 D chains join the 1 D chains into 3 D supramolecular structure. The fluorescence property has been studied and could be attributed to the π~*→π transitions of ligands.
One chain-like coordination polymer [Pb( TP)( 2,2'-bipy) ]n( TP = terephthalic acid,2,2 '-bipy = 2,2'-bipyridine) was synthesized under of hydrothermal reaction based on lead nitrate,terephthalic acid and 2,2 '-bipyridine. The structure and properties of the target complex were characterized by X-ray single crystal diffraction,EA,IR and fluorescence analysis. The X-ray crystallographic analysis reveals that complex 1 crystallizes in the triclinic system,space group P-1. The crystal cell parameters are a = 0. 9444 nm,b = 0. 95273 nm,c =1. 04054 nm,α = 113. 179( 3) °,β = 80. 0140( 3) °,γ = 100. 774( 3) °,V = 0. 80677 nm~3,Z = 2,respectively.Both the two carboxylate groups of TP are adopt chelated coordination mode linking two Pb2 +ions forming a 1 D zigzag-like chain along a axis. The π-π packing interactions between the 2,2 '-bipy ligands from the adjacent 1 D chains join the 1 D chains into 3 D supramolecular structure. The fluorescence property has been studied and could be attributed to the π~*→π transitions of ligands.
引文
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[7]Liang L L,Gao Y Y,Yue q,et al. Photoluminescence,magnetic and photocatalytic properties of three overlapping layered homochiral coordination polymers based on semi-rigid alanine ligands[J]. Inorg. Chim. Acta,2017,461:102-110.
[8]Hou J J,Zhang R,Qin Y L,et al. From(3,6)-Connected kgd,chiral anh to(3,8)-connected tfzd nets in low nuclear metal cluster-based networks with triangular pyridinedicarboxylate ligand[J]. Cryst. Growth Des.,2013,13(4):1618-1625.
[9]Hou L,Liu B,Jia L,et al. Two new(3,6)-connected frameworks based on an unsymmetrical tritopic pyridyl-dicarboxylate ligand and CO2dimer:structures,magnetic,and sorption properties[J]. Cryst. Growth Des,2013,13(2):701-707.
[10]Liu B,Zhou H F,Hou L,et al. Structural diversity of cadmium(II)coordination polymers Induced by tuning the coordination sites of Isomeric ligands[J]. Inorg. Chem. 2016,55(17):8871-8880.
[11]Zhou X H,Chen Q Q,Liu B L,et al. Syntheses,structures and magnetic properties of nine coordination polymers based on terphenyl-tetracarboxylic acid ligands[J]. Dalton Trans.,2017,46(2):430-444.
[12]McKinstry R,Cathcart R J,Cussen E J,et al. Scalable continuous solvothermal synthesis of metal organic framework(MOF-5)crystals[J]. Chem. Eng. J.,2016,285:718-725.
[13]Han M,Bai L,Tang P,et al. Biphenyl-2,4,6,3’,5’-pentacarboxylic acid as a tecton for six new Co(II)coordination polymers:p H and N-donor ligand-dependent assemblies,structure diversities and magnetic properties[J]. Dalton Trans.,2015,44(33):14673-14685.
[14]Gu J Z,Cui Y H,Liang X X,et al. Structurally Distinct Metal Organic H-Bonded Networks Derived from 5(6-Carboxypyridin-3-yl)isophthalic Acid:Coordination and Template Effect of 4,4'-Bipyridine[J]. Cryst. Growth Des. 2016,16(8):4658-4670.
[15]Sheldrick G M. SHELXS-97,Program for crystal structure solution[M]. Germany University of Gttingen,1997.
[16]Sheldrick G M. SHELXL-97,Program for crystal structure refinement[M]. Germany University of Gttingen,1997.
[17]杨娟,缪娟,戴俊,等.对位取代苯甲酸与2,2’-联吡啶配体构筑的两种二价铅配合物的合成、晶体结构及性质[J].无机化学学报,2010,26(11):1992-2000.
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