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

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posted on 2003-07-17, 00:00 authored by Yonghong Wan, Liping Zhang, Linpei Jin, Song Gao, Shaozhe Lu
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.

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