Unprecedented Lanthanide-Containing Coordination Polymers Constructed from Hexanuclear Molecular Building Blocks: {[Ln₆O(OH)₈](NO₃)₂(bdc)(Hbdc)₂·2NO₃·H₂bdc}_∞

Abstract

Reactions in acetonitrile between 1,4-benzene-dicarboxylic acid (C(8)H(6)O(4)) and a hexanuclear complex of lanthanide [Ln(6)O(OH)(8)(NO(3))(6)·2NO(3)] with Ln = Y or Tb lead to 1D-coordination polymers with the general chemical formula {[Ln(6)O(OH)(8)](NO(3))(2)(bdc)(Hbdc)(2)·2NO(3)·H(2)bdc}(∞) where H(2)bdc stands for 1,4-benzene-dicarboxylic acid (or terephthalic acid). These two compounds are isostructural. The crystal structure has been solved on the basis of the X-ray powder diffraction diagram of the Y-containing compound. This compound crystallizes in the triclinic system, space group P1 (no. 2) with a = 10.4956(6) Å, b = 11.529(2) Å, c = 12.357(2) Å, α = 86.869(9)°, β = 114.272(6)°, γ = 71.624(7)°, V = 1264.02 Å(3), and Z = 2. The crystal structure can be described as the juxtaposition of linear chains of hexanuclear entities linked to each other by terephthalate ligands. Two additional partially protonated terephthalate ligands spreading laterally to the chain are bound to each hexanuclear entity. Another diprotonated terephthalic ligand and two nitrate ions ensuring the electroneutrality of the crystal structure lie in the interchain space. These two compounds are thermally stable until 200 °C. Thanks to a so-called antenna effect, the Tb-containing compound, despite short intermetallic distances, exhibits a strong luminescence under UV irradiation.

Variation of structural motifs in lanthanoid hydroxo clusters by ligand modification

“…The controlled hydrolysis approach to obtain lanthanoid clusters has also been achieved in the absence of protecting ligands. 4,6,[12][13][14][15][16][17] In this case, the pH is slowly raised by the addition of a diluted base (often aqueous NaOH) to the point where the solution becomes persistently turbid. This point is identified as the pH where the equilibrium has reached initial precipitation of lanthanoid hydroxide.…”

Characterization and Luminescence Properties of Lanthanide-Based Polynuclear Complexes Nanoaggregates

“…38 These complexes have been proved to be usable as molecular precursors, 41 and coordination polymers in which they act as metallic centers have been synthesized and structurally characterized. 43 These coordination polymers exhibit unique luminescence properties. 44,45 Despite these promising results, it must be noticed that these hexanuclear complexes present weak stability in moist media and in most usual polar organic solvents (see Supporting Information, Table S1).…”

Isoreticular Lanthanide Metal‐Organic Frameworks: Syntheses, Structures and Photoluminescence of a Family of 3D Phenylcarboxylates

“…So although numerous studies show the relationship between structure and properties in a variety of LnMOFs,3g,5 many more examples are needed to highlight useful trends and derive the principles that can instruct the tailoring of targeted frameworks. In studies so far, multifunctional carboxylates such as 1,4‐benzenedicarboxylate (bdc)1b,1m,1p,6 and 4,4′‐biphenyldicarboxylate (bpdc)1m,1p,7 are very popular because they display multiple coordination modes, form stable complexes with Ln III ions and display π‐stacking effects that help to direct the formation of well‐defined structures. Recently, a number of LnMOF papers have reported structures that contain the formate ion (HCOO – ),5g,8 the smallest carboxylate.…”