High-Dimensional Architectures from the Self-Assembly of Lanthanide Ions with Benzenedicarboxylates and 1,10-Phenanthroline

Six new coordination polymers, [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), and
[Yb2(1,4-BDC)3(phen)2(H2O)]n (6), were synthesized by hydrothermal reactions of lanthanide chlorides with three
isomers of benzenedicarboxylic acid (H2BDC) 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 π−π 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 P21/c, with a = 12.565(6) Å, b = 16.005(8) Å, c = 12.891(6) Å, β = 102.173(8)°, and Z = 4; for 2,
monoclinic, space group P21/c, with a = 20.979(4) Å, b = 11.5989(19) Å, c = 20.810(3) Å, β = 110.391(3)°, and
Z = 4; for 3, triclinic, space group P1̄, with 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)°, and Z = 2; for 4, triclinic, space group P1̄, with 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)°, and Z = 2; for 5, orthorhombic, space
group C2221, with a = 8.174(2) Å, b = 24.497(7) Å, c = 29.161(8) Å, and Z = 8; for 6, triclinic, space group P1̄,
with 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)°, and
Z = 2. The magnetic properties of 1 and 4 were investigated. The photophysical properties of 1 were also studied.

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) 以及 [Yb2(1,4-BDC)3(phen)2(H2O)]n (6)，通过稀土氯化物与苯二羧酸的三种异构体 (H2BDC) 及 1,10-菲罗啉 (phen) 的水热反应合成，并采用单晶X射线衍射技术进行表征。其中，1 具有二维的人字架构和Z形空腔。2 和 5 构成不同的三维网络，均由1,3-BDC阴离子通过羧酸基团桥接金属中心（Eu或Yb）。3 和 6 拥有相似的层状结构，通过氢键和/或π-π芳香相互作用进一步构建成三维网络。4 由一维链构成，通过氢键进一步连接，形成三维网络。在三种铕配合物中，所有铕离子均为八配位，而其他三种三配位聚合物中钇离子配位数介于六至八之间。晶体数据：对于 1，单斜晶系，空间群 P21/c，晶胞参数为 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 P21/c，晶胞参数为 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 P1̄，晶胞参数为 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 P1̄，晶胞参数为 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 C2221，晶胞参数为 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 P1̄，晶胞参数为 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。对 1 和 4 的磁性质进行了研究。同时，对 1 的光物理性质也进行了探讨。