含有刚柔混合多羧酸配体的稀土配位聚合物的合成、结构及荧光性能
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摘要
以柔性的氨基三乙酸为第一配体,具有特殊刚性平面结构的草酸为第二配体,采用水热合成法在自生压力下与稀土硝酸盐自组装合成了两个新的三维网状含刚柔混合多羧酸稀土配位聚合物[KLn_2(NTA)(ox)_2(H_2O)_5]_n(Ln=Ce(1),Tb(2);H_3NTA=氨基三乙酸,H_2ox=草酸),并对化合物1和2进行了X射线单晶结构解析、元素分析、红外和热分析等表征。X射线单晶衍射数据解析表明化合物1和2是同构的,属于单斜晶系,P2(1)/m空间群。在两个化合物的三维网状结构中,存在着沿a轴方向的一维的孔道。拓扑学分析发现,化合物1和2具有两个4-连接的无机节点和一个4-连接的有机节点,形成了少有的三维(4,4,4)-连接的多孔网络拓扑结构。对化合物2进行固态荧光光谱分析,结果显示化合物2在340 nm的激发波长作用下,能够产生强的Tb~(3+)特征发射跃迁,发出较纯的绿光。
Utilized the hydrothermal synthesis method,two new isomorphic 3D lanthanide coordination polymers[KLn_2(NTA)(ox)_2(H_2O)_5]_n(Ln = Ce(1) and Tb(2); H_3 NTA = nitrilotriacetic acid,H_2ox = oxalic acid)were synthesized by self-assembly of lanthanide nitrate( cerium nitrate,terbium nitrate) with NTA and ox ligands.The structures of the two compounds were characterized by X-ray single crystal diffraction,elemental analysis,IR spectrum and TG. The X-ray single crystal diffraction data analyses revealed that compounds 1 and 2 were isomorphic,belonged to the monoclinic system,P2(1)/m space group,and there existed 1D channels along the two axis in its 3D structure. Additionally,through a topological approach,we can define a 4-link organic node and two 4-link inorganic nodes,which formed a rare 3D(4,4,4)-connected porous network topology structure. Furthermore,the fluorescence property of compound 2 was investigated in the visible region at the room temperature.The photoluminescence analysis indicated that the compound 2 exhibits the characteristic transitions of the Tb~(3+)ion,and emits green light with maxima at 543 nm( λ_(ex)= 340 nm).
Utilized the hydrothermal synthesis method,two new isomorphic 3D lanthanide coordination polymers[KLn_2(NTA)(ox)_2(H_2O)_5]_n(Ln = Ce(1) and Tb(2); H_3 NTA = nitrilotriacetic acid,H_2ox = oxalic acid)were synthesized by self-assembly of lanthanide nitrate( cerium nitrate,terbium nitrate) with NTA and ox ligands.The structures of the two compounds were characterized by X-ray single crystal diffraction,elemental analysis,IR spectrum and TG. The X-ray single crystal diffraction data analyses revealed that compounds 1 and 2 were isomorphic,belonged to the monoclinic system,P2(1)/m space group,and there existed 1D channels along the two axis in its 3D structure. Additionally,through a topological approach,we can define a 4-link organic node and two 4-link inorganic nodes,which formed a rare 3D(4,4,4)-connected porous network topology structure. Furthermore,the fluorescence property of compound 2 was investigated in the visible region at the room temperature.The photoluminescence analysis indicated that the compound 2 exhibits the characteristic transitions of the Tb~(3+)ion,and emits green light with maxima at 543 nm( λ_(ex)= 340 nm).
引文
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[19]Zhao D,Rao X T,Yu J C,Cui Y J,Yang Y,Qian G D.Syntheses,structures and tunable luminescence of lanthanide metal-organic frameworks based on azole-containing carboxylic acid ligand[J].J.Solid State Chem.,2015,230:287.
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[21]吕志军,魏长平,任晓明,程卫国.新型稀土Eu,Tb(Ⅲ)芳香羧酸配合物的合成及发光性能[J].中国稀土学报,2012,30(4):410.LüZ J,Wei C P,Ren X M,Cheng W G.Synthesis and fluorescence property of novel rare earth europium,terbium(Ⅲ)ternary complexes with aromatic carboxylic acid[J].Journal of the Chinese Society of Rare Earths,2012,30(4):410.
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[23]王晓中,杨庆凤,章月平,王政,刘万毅,冀永强.由混合羧酸构筑的稀土配位聚合物的合成[J].辽东学院学报(自然科学版),2011,18(04):265.Wang X Z,Yang Q F,Zhang Y P,Wang Z,Liu W Y,Ji Y Q.Synthesis of a rare-earth coordination polymer constructed from mixed dicarboxylate ligands[J].Journal of Eastern Liaoning University(Natural Science),2011,18(4):265.
[24]Wang Z,Zhang H H,Chen Y P,Huang C C,Sun R Q,Cao Y N,Yu X H.Two fluorescent coordination polymers constructed from mixed rigid and flexible carboxylate ligands:Formation of cross-linking helical and zigzag chains[J].J.Solid State Chem.,2006,179(5):1536.
[25]Xie Y,Xing Y H,Wang Z,Zhao H Y,Zeng X Q,Ge M F,Niu S Y.Synthesis,structures and luminescent properties of novel coordination polymers constructed by lanthanide salts and benzimidazole-5,6-dicarboxylic acid[J].Inorg.Chim.Acta,2010,363(5):918.
[26]刘云晶,钟昀,方智利.稀土Sm-1,3,5-三[4-苯甲酸]-均苯三甲酰胺配合物的合成、结构及性质研究[J].中国稀土学报,2015,33(1):66.Liu Y J,Zhong Y,Fang Z L.Synthesis,crystal structures and properties of rare earth coordination polymer Sm-1,3,5-tri[4-benzoic]-benzenetriyl-tris(formamide)[J].Journal of the Chinese Society of Rare Earths,2015,33(01):66.
[27]邓圣军,陈杰,钱浩,张宁.Nd/Eu混合稀土配位聚合物的原位合成及光致发光性质研究[J].中国稀土学报,2015,33(6):663.Deng S J,Chen J,Qian H,Zhang N.In situ synthesis and photoluminescence properties of Nd/Eu mixed rare earths coordination polymers[J].Journal of the Chinese Society of Rare Earths,2015,33(6):663.
[2]Fang M,Chen Z,Yin G W,Kang X M,Xu H.Novel lanthanide coordination polymers with Eu-compound exhibits warm white light emission:Synthesis,structure,and magnetic properties[J].Inorg.Chem.Commun.,2016,70:51.
[3]Song C Y,L X H,Liu W,Cao Z Q,Ren Y Y,Zhou Q C,Zhang L.Construction of three new lanthanide-organic frameworks with(3,6)-connected rtl-type topology[J].Synth.React.Inorg.Met.-Org.Chem.,2016,46(8):1174.
[4]Wang J L,Hou K L,Bai F Y,Xing Y H,Shi Z.Hydrothermal synthesis,crystal structure,and photoluminescence of novel lanthanide metal organic frameworks constructed from 1,4-benzene-dicarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid as ligands[J].Struct.Chem.,2012,23(1):275.
[5]Du R Z,Wang Y Y,Xie Y Y,Li H T,Liu T F.Synthesis and crystal structure of new lanthanide coordination polymers with Pyridine-2,6-dicarboxylic acid[J].J.Mol.Struct.,2016,1108(15):96.
[6]Weng H,Yan B.Lanthanide coordination polymers for multi-color luminescence and sensing of Fe3+[J].Inorg.Chem.Commun.,2016,63:11.
[7]Wang S Y,Xu J L,Shan L,Wang L,Song T Y,Zhang C H,Chen X D,Fan Y.3D lanthanide coordination polymers constructed from polynuclear clusters and Vshaped organic connectors:Syntheses,structures and properties[J].Inorg.Chim.Acta,2015,427(1):118.
[8]Hu M,Zhao H,Sa1udo E C,Chen M.Four lanthanide-carboxylate coordination polymers with mixed 2,3-naphthalenedicarboxylate and phen ligands:Syntheses,structures,luminescent and magnetic properties[J].Polyhedron,2015,101(24):270.
[9]Wang Q,Fan Y,Song T Y,Xu J N,Wang J,Chai J,Liu Y L,Wang L,Zhang L R.In situ synthesis of a series of lanthanide coordination polymers based on Nheterocyclic carboxylate ligands:Crystal structure and luminescence[J].Inorg.Chim.Acta,2015,438(1):128.
[10]Almá3i M,Zeleňák V,Opanasenko M,CísarˇováI.Ce(III)and Lu(III)metal-organic frameworks with Lewis acid metal sites:Preparation,sorption properties and catalytic activity in Knoevenagel condensation[J].Catal.Today,2015,243(1):184.
[11]Cui Y J,Chen B L,Qian G D.Lanthanide metal-organic frameworks for luminescent sensing and light-emitting applications[J].Coord.Chem.Rev.,2014,273-274(15):76.
[12]Zhang J,Huang J,Yang J,Chen H J.Two-and three-dimensional lanthanide metal-organic frameworks with hydroxyl-functionalized nicotinic acid and oxalate ligands[J].Inorg.Chem.Commun.,2012,17:163.
[13]Li B,Wen H M,Cui Y J,Qian G D,Chen B L.Multifunctional lanthanide coordination polymers[J].Prog.Polym.Sci.,2015,48:40.
[14]王卓,白凤英,邢永恒,谢妍,赵海燕,施展.含有刚柔混合多羧酸配体的新型稀土配位聚合物[Ce(pydc)(Hglu)]n的水热合成、结构和性质[J].无机化学学报,2010,26(8):1503.Wang Z,Bai F Y,Xing Y H,Xie Y,Zhao H Y,Shi Z.Lanthanide complexes containing both rigid and flexible as mixed ligands[Ce(pydc)(Hglu)]n:Synthesis,structure and property[J].Chinese Journal of Inorganic Chemistry,2010,26(08):1503.
[15]Zhang Y,Luo W P,Liu D G,Xu Y,Li S L,Li J F,Wu Y,Zhou Y M,Fang M,Liu H.Structures and photoluminescence properties of two cadmium(II)coordination polymers synthesized by flexible and rigid ligands[J].Inorg.Chim.Acta,2014,409:512.
[16]Wu G Y,Ren Y X,Yin Z,Sun F,Zeng M H,Kurmoo M.Effects of substituent groups on the structures and luminescence properties of 2D/3D Cd II complexes with mixed rigid and flexible carboxylate ligands[J].RSC Adv.,2014,4(46):24183.
[17]Ay B,Karaca S,Yildiz E,Lopez V,Nanao M H,Zubieta J.In situ hydrothermal syntheses,structures and photoluminescent properties of four novel metal-organic frameworks constructed by lanthanide(Ln=Ce(III),Pr(III),Eu(III))and Cu(I)metals with flexible dicarboxylate acids and piperazine-based ligands[J].J.Solid State Chem.,2016,233:415.
[18]Chen M,Hu M,Xu W M,Sa1udo E C,Fang S M,Liu C S.Six lanthanide supramolecular frameworks based on mixed m-/p-hydroxybenzoic acid and 1,10-phenanthroline tectons:Syntheses,crystal structures,and properties[J].Polyhedron,2016,113:132.
[19]Zhao D,Rao X T,Yu J C,Cui Y J,Yang Y,Qian G D.Syntheses,structures and tunable luminescence of lanthanide metal-organic frameworks based on azole-containing carboxylic acid ligand[J].J.Solid State Chem.,2015,230:287.
[20]Zhou X H,Li L,Li A,Yang T,Huang W.Three-dimensional lanthanide metal-organic frameworks with the fluorene-based carboxylate ligands:Syntheses,structures,and properties[J].Inorg.Chim.Acta,2014,413(24):38.
[21]吕志军,魏长平,任晓明,程卫国.新型稀土Eu,Tb(Ⅲ)芳香羧酸配合物的合成及发光性能[J].中国稀土学报,2012,30(4):410.LüZ J,Wei C P,Ren X M,Cheng W G.Synthesis and fluorescence property of novel rare earth europium,terbium(Ⅲ)ternary complexes with aromatic carboxylic acid[J].Journal of the Chinese Society of Rare Earths,2012,30(4):410.
[22]Yang Q F,Cui X B,Chen Y,Wang Z,Yu J H,Xu JQ,Wang T G.Two new 3D lanthanide metal-organic frameworks constructed from nitrilotriacetate and oxalate ligands[J].Inorg.Chem.Commun.,2011,14(1):320.
[23]王晓中,杨庆凤,章月平,王政,刘万毅,冀永强.由混合羧酸构筑的稀土配位聚合物的合成[J].辽东学院学报(自然科学版),2011,18(04):265.Wang X Z,Yang Q F,Zhang Y P,Wang Z,Liu W Y,Ji Y Q.Synthesis of a rare-earth coordination polymer constructed from mixed dicarboxylate ligands[J].Journal of Eastern Liaoning University(Natural Science),2011,18(4):265.
[24]Wang Z,Zhang H H,Chen Y P,Huang C C,Sun R Q,Cao Y N,Yu X H.Two fluorescent coordination polymers constructed from mixed rigid and flexible carboxylate ligands:Formation of cross-linking helical and zigzag chains[J].J.Solid State Chem.,2006,179(5):1536.
[25]Xie Y,Xing Y H,Wang Z,Zhao H Y,Zeng X Q,Ge M F,Niu S Y.Synthesis,structures and luminescent properties of novel coordination polymers constructed by lanthanide salts and benzimidazole-5,6-dicarboxylic acid[J].Inorg.Chim.Acta,2010,363(5):918.
[26]刘云晶,钟昀,方智利.稀土Sm-1,3,5-三[4-苯甲酸]-均苯三甲酰胺配合物的合成、结构及性质研究[J].中国稀土学报,2015,33(1):66.Liu Y J,Zhong Y,Fang Z L.Synthesis,crystal structures and properties of rare earth coordination polymer Sm-1,3,5-tri[4-benzoic]-benzenetriyl-tris(formamide)[J].Journal of the Chinese Society of Rare Earths,2015,33(01):66.
[27]邓圣军,陈杰,钱浩,张宁.Nd/Eu混合稀土配位聚合物的原位合成及光致发光性质研究[J].中国稀土学报,2015,33(6):663.Deng S J,Chen J,Qian H,Zhang N.In situ synthesis and photoluminescence properties of Nd/Eu mixed rare earths coordination polymers[J].Journal of the Chinese Society of Rare Earths,2015,33(6):663.