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

Abstract

Six new coordination polymers, [Eu(1,2-BDC)(1,2-HBDC)(phen)(H(2)O)](n) (1), [Eu(2)(1,3-BDC)(3)(phen)(2)(H(2)O)(2)](n).4nH(2)O (2), [Eu(1,4-BDC)(3/2)(phen)(H(2)O)](n) (3), [Yb(2)(1,2-BDC)(3)(phen)(H(2)O)(2)](n).3.5nH(2)O (4), [Yb(2)(1,3-BDC)(3)(phen)(1/2)](n) (5), and [Yb(2)(1,4-BDC)(3)(phen)(2)(H(2)O)](n) (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.

Enhancement in red emission at room temperature from europium doped ZnO nanowires by 1,10 phenanthroline-europium interface induced resonant excitations

“…This is supported by previous reports on synthesis of Eu 3+ complex compound with phen or surface functionalization of Eu 3+ doped nanoparticles with phen ligand. [33][34][35][36] Here, the phen molecules are mainly attached on the surface to the europium sites by metal-ligand interfacial bonding interaction. In this work, phen is attached to the europium sites in the Eu:ZnO NWs with the aim of improvements and tuning the photo-physical properties of Eu3 + ions.…”

Crystal Structure, Spectroscopy and Crystal Field Analysis of Substituted 1,10‐Phenanthroline–Europium Complexes

“…An alternative is to employ an organic chromophore as a good light harvester to sensitize lanthanide ions (Ln 3+ ) by energy transfer, usually from the triplet state, by the antenna effect. [12][13][14][15] The ligand 1,10-phenanthroline (phen) is an excellent antenna with singlet and triplet states at 29200 and 22100 cm -1 ,…”

A New Family of Heterometallic LnIII[12-MCFeIIIN(shi)-4] Complexes: Syntheses, Structures and Magnetic Properties

“…The ground state of Eu III ion is 7 F 0 and the configuration is 4 f 6 ( 7 F 0 , S = 3, L = 3, J = 0). At a low temperature, only the infinitesimal excited states mixing into 7 F 0 [46] occupied the nonmagnetic ground level. Thus, the magnetic properties of complex 1 at a low temperature are mainly caused by the exchange interaction between Fe III ions.…”