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Three resorcin[4]arene-based lanthanide-coordination polymers with multifunctional photoluminescence sensing properties.

ABSTRACT: By utilizing a novel octacarboxylate-functionalized resorcin[4]arene as organic linkers, three lanthanide-coordination polymers, namely, [(CH₃)₂NH₂][Ln₂(HL)(H₂O)₇]·2H₂O (Ln = Tb (1), Eu (2) and Gd (3), H₈L = 2,8,14,20-tetra-pentyl-4,6,10,12,16,18,22,24-octa-carboxymethoxy-resorcin[4]arene) have been solvothermally synthesized and structurally characterized. Isostructural 1-3 display unique two dimensional sandwich-based layers built with Ln³⁺ cations and bowl-shaped HL^7- anions. Remarkably, 1 and 2 produce intensive green and red emissions respectively and long lifetimes thanks to the antenna effect of HL^7- anions. The energy level testing of 3 indicates that the newly designed ligand H₈L has a very efficient intersystem crossing process. More importantly, luminescent investigations reveal that 1 and 2 can selectively detect N,N'-dimethylformamide and Fe³⁺ ions with turn-on-type and turn-off-type responses, respectively.

SUBMITTER: Zhang H

PROVIDER: S-EPMC9060889 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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Three resorcin[4]arene-based lanthanide-coordination polymers with multifunctional photoluminescence sensing properties.

Zhang Hang H Wang Jia-Chen JC Jiang Wei W Zhao Si-Si SS

RSC advances 20190128 7

By utilizing a novel octacarboxylate-functionalized resorcin[4]arene as organic linkers, three lanthanide-coordination polymers, namely, [(CH3)2NH2][Ln2(HL)(H2O)7]·2H2O (Ln = Tb (1), Eu (2) and Gd (3), H8L = 2,8,14,20-tetra-pentyl-4,6,10,12,16,18,22,24-octa-carboxymethoxy-resorcin[4]arene) have been solvothermally synthesized and structurally characterized. Isostructural 1-3 display unique two dimensional san ...[more]

PMID: 35518116

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Project description:The influence of synthetic conditions on the solid-state structural formation of lanthanide(iii) complexes based on a hydrazide ligand have been investigated and reported. Depending on the solvents and reaction temperatures, the reactions of hydrated Ln(NO3)3 with a benzohydrazide (bzz) ligand afforded three classes of lanthanide(iii) coordination complexes viz. [Ln(bzz)(NO3)](NO3)2 (1Ln; Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5)), [Ln(bzz)(ben)3(H2O)]·H2O (2Ln; Ln = Pr (6), Nd (7), Sm (8), Eu (9), Gd (10), Tb (11), Dy (12), Er (13)), and [Ln3(ben)3] (3Ln; Ln = Eu (14), Gd (15), Tb (16), Dy (17), Er (18), Tm (19), Yb (20), Lu (21)). Complexes 1-5 in series 1Ln were isolated by slow evaporation of their isopropanol solutions at ambient temperature, and the complexes display similar discrete structures bearing distinct intermolecular N-H⋯O hydrogen bonds to generate a three-dimensional (3D) supramolecular architecture. Complexes 6-13 in series 2Ln were obtained under hydrothermal conditions at 110 °C where the in situ generated benzoate (ben) ligands participated in the formation of one-dimensional (1D) coordination polymers (CPs) with the bzz ligands. At a temperature of 145 °C the hydrothermal conditions result in the formation of the thermodynamically more stable products of 14-21 in series 3Ln, in which the bzz ligand underwent complete in situ hydrolysis to create the ben ligand. These coordination assemblies feature 1D zigzag chains that are formed by unusual low coordination numbers of the six- and seven-fold coordinated Ln3+ centers bridged by the ben ligands in μ 2- and μ 3-coordination modes. Notably, the chain structures of 2Ln can be transformed into the zigzag tape-like structures of 3Ln upon heating the crystalline samples to 400 °C in air. In the solid state at room temperature, the Eu- (2, 9, 14) and Tb- (4, 11, 16) containing complexes emit red and green light, respectively. The luminescence investigations show that the Eu- (9, 14) and Tb-(11, 16) based CPs could be used as fluorescent probes for acetone and Co2+ ions via an energy competition mechanism. Meanwhile, the Gd- (10, 15) and Dy- (12, 17) based CPs show typical antiferromagnetic interactions.

Dataset Information

Three resorcin[4]arene-based lanthanide-coordination polymers with multifunctional photoluminescence sensing properties.

Publications

Three resorcin[4]arene-based lanthanide-coordination polymers with multifunctional photoluminescence sensing properties.

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