镧系离子与苯二甲酸酯和1,10-菲咯啉自组装形成的高维结构。

High-dimensional architectures from the self-assembly of lanthanide ions with benzenedicarboxylates and 1,10-phenanthroline.

作者信息

Wan Yonghong, Zhang Liping, Jin Linpei, Gao Song, Lu Shaozhe

机构信息

Department of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China.

出版信息

Inorg Chem. 2003 Aug 11;42(16):4985-94. doi: 10.1021/ic034258c.

DOI:10.1021/ic034258c

PMID:12895124

Abstract

Six new coordination polymers, Eu(1,2-BDC)(1,2-HBDC)(phen)(H(2)O) (1), Eu(2)(1,3-BDC)(3)(phen)(2)(H(2)O)(2).4nH(2)O (2), Eu(1,4-BDC)(3/2)(phen)(H(2)O) (3), Yb(2)(1,2-BDC)(3)(phen)(H(2)O)(2).3.5nH(2)O (4), Yb(2)(1,3-BDC)(3)(phen)(1/2) (5), and Yb(2)(1,4-BDC)(3)(phen)(2)(H(2)O) (6), were synthesized by hydrothermal reactions of lanthanide chlorides with three isomers of benzenedicarboxylic acid (H(2)BDC) and 1,10-phenanthroline (phen), and characterized by single-crystal X-ray diffraction. 1 has a 2-D herringbone architecture with a Z-shaped cavity. 2 and 5 have different 3-D networks, but both are formed by 1,3-BDC anions bridging metal centers (Eu or Yb) via carboxylate groups. 3 and 6 possess similar layer structures which are further constructed to form 3-D networks by hydrogen bonds and/or pi-pi aromatic interactions. 4 comprises 1-D chains that are further interlinked via hydrogen bonds, resulting in a 3-D network. In the three europium complexes, all the europium ions are eight-coordinated, while the coordination numbers of the ytterbium ions in other three-coordination polymers range from six to eight. Crystal data: for 1, monoclinic, space group P2(1)/c, with a = 12.565(6) A, b = 16.005(8) A, c = 12.891(6) A, beta = 102.173(8) degrees, and Z = 4; for 2, monoclinic, space group P2(1)/c, with a = 20.979(4) A, b = 11.5989(19) A, c = 20.810(3) A, beta = 110.391(3) degrees, and Z = 4; for 3, triclinic, space group P1, with a = 10.331(5) A, b = 10.887(5) A, c = 11.404(5) A, alpha = 107.660(7) degrees, beta = 91.787(7) degrees, gamma = 112.946(6) degrees, and Z = 2; for 4, triclinic, space group P1, with a = 11.517(5) A, b = 13.339(5) A, c = 13.595(6) A, alpha = 87.888(7) degrees, beta = 67.759(6) degrees, gamma = 68.070(6) degrees, and Z = 2; for 5, orthorhombic, space group C222(1), with a = 8.174(2) A, b = 24.497(7) A, c = 29.161(8) A, and Z = 8; for 6, triclinic, space group P1, with a = 10.349(3) A, b = 11.052(3) A, c = 19.431(6) A, alpha = 105.464(4) degrees, beta = 91.300(5) degrees, gamma = 93.655(5) degrees, and Z = 2. The magnetic properties of 1 and 4 were investigated. The photophysical properties of 1 were also studied.

摘要

通过镧系氯化物与苯二甲酸（H₂BDC）的三种异构体以及1,10 - 菲咯啉（phen）的水热反应，合成了六种新型配位聚合物，[Eu(1,2 - BDC)(1,2 - HBDC)(phen)(H₂O)]ₙ (1)、[Eu₂(1,3 - BDC)₃(phen)₂(H₂O)₂]ₙ·4nH₂O (2)、[Eu(1,4 - BDC)³/₂(phen)(H₂O)]ₙ (3)、[Yb₂(1,2 - BDC)₃(phen)(H₂O)₂]ₙ·3.5nH₂O (4)、[Yb₂(1,3 - BDC)₃(phen)¹/₂]ₙ (5) 和 [Yb₂(1,4 - BDC)₃(phen)₂(H₂O)]ₙ (6)，并通过单晶X射线衍射对其进行了表征。1具有二维人字形结构和Z形空腔。2和5具有不同的三维网络结构，但二者均由1,3 - BDC阴离子通过羧酸根基团桥连金属中心（Eu或Yb）形成。3和6具有相似的层状结构，这些层状结构通过氢键和/或π - π芳香相互作用进一步构建形成三维网络。4由一维链组成，这些链通过氢键进一步相互连接，形成三维网络。在三种铕配合物中，所有铕离子均为八配位，而其他三种镱配位聚合物中镱离子的配位数在六到八之间。晶体数据：对于1，单斜晶系，空间群P2(1)/c，a = 12.565(6) Å，b = 16.005(8) Å，c = 12.891(6) Å，β = 102.173(8)°，Z = 4；对于2，单斜晶系，空间群P2(1)/c，a = 20.979(4) Å，b = 11.5989(19) Å，c = 20.810(3) Å，β = 110.391(3)°，Z = 4；对于3，三斜晶系，空间群P1，a = 10.331(5) Å，b = 10.887(5) Å，c = 11.404(5) Å，α = 107.660(7)°，β = 91.787(7)°，γ = 112.946(6)°，Z = 2；对于4，三斜晶系，空间群P1，a = 11.517(5) Å，b = 13.339(5) Å，c = 13.595(6) Å，α = 87.888(7)°，β = 67.759(6)°，γ = 68.070(6)°，Z = 2；对于5，正交晶系，空间群C222(1)，a = 8.174(2) Å，b = 24.497(7) Å，c = 29.161(8) Å，Z = 8；对于6，三斜晶系，空间群P1，a = 10.349(3) Å，b = 11.052(3) Å，c = 19.431(6) Å，α = 105.464(4)°，β = 91.300(5)°，γ = 93.655(5)°，Z = 2。研究了1和4的磁性质。还研究了1的光物理性质。