用高氯酸铕和3,5-吡啶二甲酸、2,4,6-吡啶三甲酸在水热条件下反应合成了一个含有两种吡啶多羧酸阴离子配体的三维配位聚合物{[Eu2(2,4,6-Hptc)(3,5-pdc)2(H2O)8]·6H2O}n(1)(2,4,6-H3ptc =2,4,6-吡啶三甲酸；3,5-H2 pdc =3,5-吡啶二甲酸)。单晶X-射线衍射分析表明,该配合物属单斜晶系,C2/c空间群,晶胞参数为a=2.0106(11) nm,b=1.1048(6) nm,c=1.7591(10) nm,β=112.117(8)°,α=γ=90°。配合物的中心Eu3+与九个氧原子配位,其中五个氧原子来自配体羧基氧原子,四个来自配位水分子,这些氧原子形成了变形三帽三棱柱结构。3,5-pdc阴离子的两个羧酸根分别以螯合方式连接两个Eu3+,形成一维链状结构。2,4,6-Hptc以铵盐形式用2-和6-位羧基配位,4-位羧基没有与金属离子配位,通过2,4,6-Hptc的配位将由3,5-pdc与Eu3+形成的一维链连接成一维梯状链结构。该配合物在紫外光的激发下显示红色荧光,具有良好的光致发光性质。
A 3D europium coordination polymer {[Eu2(2,4,6-Hptc)( 3,5-pdc)2(H2O)8]·6H2O}n(1) (2, 4, 6-H3 ptc = 2, 4, 6-pyridinetricarboxylic acid;3, 5-H2 pdc = 3, 5-pyridinedicarboxylic acid ) was synthesized by hydrothermal method using europium perchlorate reacting with 3,5-pyridinedicarboxylic acid and 2,4,6-pyridinetricarboxylic acid. X-ray diffraction analysis of single crystal shows that the complex is crystallized in monoclinic system, C2/c space group. The cell parameters are as follows a=2. 0106(11) nm,b=1. 1048(6) nm,c=1. 7591(10) nm,β = 112. 117(8) °,α = γ = 90°. Eu3+ ions in the complex is coordinated with nine oxygen atoms. Five O atmos are from the carboxylate of lignds and the other four O atoms are from coordination water molecules. They are formed a distorted tricapped trigonal prism. The two carboxylates of each 3,5-pdc anion coordinates with Eu3+ by chelating way and a 1D chain structure is formed. 2,4,6-Hptc anions coordinate with Eu3+ by the 2-and 4-carboxylates. The 4-carboxylate does not coordinate. The 1D chain structres formed with 3,5-pdc anions and Eu3+ are further connected by 2,4,6-Hptc anions and 1D ladder shaped structure are constructed. The complex exhibits intense characteristic luminescence of Eu3+ with excitation of UV-rays.
参考文献
| [1] | Xu, W.;Zhou, Y.;Huang, D.;Xiong, W.;Su, M.;Wang, K.;Han, S.;Hong, M..Crystal structure, multiplex photoluminescence, and magnetic properties of a series of lanthanide coordination polymers based on quinoline carboxylate ligand[J].Crystal growth & design,201312(12):5420-5432. |
| [2] | 洪广言.稀土发光材料的研究进展[J].人工晶体学报,2015(10):2641-2651. |
| [3] | 王宏胜;夏军;张万强.2D配位聚合物{[Eu（pdc）（ox）0.5（H2O）4]·2H2O}n的结构和荧光性质[J].人工晶体学报,2015(1):280-286. |
| [4] | 位霄鹏;高保娇;张瑞霞.芳羧酸功能化的聚苯乙烯与Tb（Ⅲ）离子形成的高分子-稀土配合物的荧光发射性能[J].发光学报,2012(2):139-145. |
| [5] | Feng, X.;Ma, L.-F.;Liu, L.;Wang, L.-Y.;Song, H.-L.;Xie, S.-Y..A series of heterometallic three-dimensional frameworks constructed from imidazole-dicarboxylate: Structures, luminescence, and magnetic properties[J].Crystal growth & design,201310(10):4469-4479. |
| [6] | Feng, X.;Ling, X.-L.;Liu, L.;Song, H.-L.;Wang, L.-Y.;Ng, S.-W.;Su, B.Y..A series of 3D lanthanide frameworks constructed from aromatic multi-carboxylate ligand: Structural diversity, luminescence and magnetic properties[J].Dalton transactions: An international journal of inorganic chemistry,201328(28):10292-10303. |
| [7] | 王宏胜;王磊;李公春;李影影;黄保军;吴长增.1D配合物[Tb（3,5-pdc）（3,5-Hpdc）（H2O） （phen）]n的合成、晶体结构及发光性质[J].发光学报,2015(1):50-56. |
| [8] | 黄昌龙;王宏胜;李公春;田孝旭.高锰酸钾氧化法制备3,5-吡啶二甲酸[J].河北化工,2012(5):44-45,50. |
| [9] | Wang HS;Zhao B;Zhai B;Shi W;Cheng P;Liao DZ;Yan SP.Syntheses, structures, and photoluminescence of one-dimensional lanthanide coordination polymers with 2,4,6-pyridinetricarboxylic acid[J].Crystal growth & design,20079(9):1851-1857. |
| [10] | HONGSHENG WANG;JUN XIA;BIN ZHA.Structures and luminescent properties of two heterotrimetallic Ln(III)-Sr(II)-K(I) complexes[J].Journal of Coordination Chemistry,201419/20(19/20):3234-3242. |
| [11] | Li CJ;Lin ZJ;Peng MX;Leng JD;Yang MM;Tong ML.Novel three-dimensional 3d-4f microporous magnets exhibiting selective gas adsorption behavior[J].Chemical communications,200847(47):6348-6350. |
| [12] | 连锡山;盛慧;刘占梅.苯甲酸稀土（Eu,La）配合物的红外和荧光光谱研究[J].光谱学与光谱分析,1999(4):562-565. |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%