Construction of lanthanide complexes supported by 2,3‐dimethoxybenzoic acid and 5,5’‐dimethy‐2,2’‐bipyridine: crystal structures, thermoanalysis, magnetic and fluorescence properties

• Published in: Applied organometallic chemistry 2019-11, Vol.33 (11), p.n/a
• Main Authors: Li, Ying‐Ying, Ren, Ning, He, Shu‐Mei, Wang, Shu‐Ping, Zhang, Jian‐Jun
• Format: Article
• Language: English
• Subjects: Chemistry; Coordination compounds; Coordination numbers; Crystal structure; Erbium; Ethanol; Fluorescence; Gadolinium; Hydrogen bonding; lanthanide complexes; Lanthanum; Ligands; Light emission; Magnetic properties; Single crystals; Thermal analysis; thermal degradation
• ISSN: 0268-2605; 1099-0739
• DOI: 10.1002/aoc.5212

A series of novel trivalent lanthanide complexes, [Ln(2,3‐DMOBA)3(5,5′‐DM‐2,2′‐bipy)]2·C2H5OH (Ln = Eu(1), Sm(2), Gd(3), Ho(4) Er(5), Pr(6), Nd(7)) (2,3‐DMOBA = 2,3‐dimethoxybenzoate, 5,5′‐DM‐2,2′‐bipy = 5,5′‐dimethy‐2,2′‐bipyridine), have been successfully synthesized and structurally validated by single crystal diffraction. All complexes discussed herein feature a binuclear structure, and contain only one free ethanol molecule, which is interesting in the lanthanide complexes. The coordination number of center Ln3+ ions is nine, showing a distorted monocapped square anti‐prismatic coordination geometry. Through a pair of alternating identical C‐H···O hydrogen bonding interactions between two 2,3‐DMOBA ligands on the same lanthanum binuclear unit with 5,5′‐DM‐2,2′‐bipy ligands on two neighboring units, the binuclear complexes can form one‐ The thermal analysis of these complexes are investigated by TG‐DSC/FTIR, the result show that the decomposition process of complexes are mainly divided into four stages with the formation of the respective oxides. The visible light emission experiment of complex 1 is carried out, and the characteristic luminescence behavior of intense red light is exhibited. What'more, fluorescence lifetimes as well as the fluorescent quantum yield of complex 1 is calculated. And the magnetic properties of complexes 3–5 are also studied. Lanthanide complexes 1–7 feature a binuclear structure, and contains one free ethanol molecule, which is relatively rare in the lanthanide complexes. Through a pair of alternating identical C‐H···O hydrogen bonding interactions between two 2,3‐DMOBA ligands on the same lanthanum binuclear unit with 5,5’‐DM‐2,2’‐bipy ligands on two neighboring units, the binuclear complexes can form one‐dimensional chain structure, and then form two‐dimensional sheet structure.