Four Dinuclear and One-Dimensional-Chain Dysprosium and Terbium Complexes Based on 2-Hydroxy-3-methoxybenzoic Acid: Structures, Fluorescence, Single-Molecule-Magnet, and Ab Initio Investigation
Zhong Li, Wen‐Bin Chen, Xiaohui Li, Zhi-Jian Ouyang, Meng Yang, Yi‐Quan Zhang, Song Gao, Wen Dong
Abstract
The unique electronic configurations of lanthanide(III) ions generate abundant electronic energy levels, resulting in the fantastic magnetic and optical multifunctional properties of lanthanide complexes. Here, 2-hydroxy-3-methoxybenzoic acid (H2MBA) was used to construct four Dy(III) and Tb(III) complexes containing two isostructural dinuclear complexes of [Ln2(HMBA)2(MBA)2(DMF)2(H2O)2]·6H2O [Ln = Dy (1), Tb (2); DMF = N,N-dimethylformamide] and two other isostructural beltlike one-dimensional-chain complexes of [NH4][Ln(HMBA)4] [Ln = Dy (3), Tb (4)]. Fluorescence measurements reveal that H2MBA can sensitize Dy(III) and Tb(III) characteristic luminescence. Furthermore, complex 3 can emit white light under UV-light irradiation originating from a dichromatic mixture of a blue emission of H2MBA and a dominating yellow emission of Dy3+ ions. Magnetic susceptibility measurements show that two Dy(III) complexes are single-molecule magnets with anisotropy barriers of 90(2) and 31(5) cm–1 for 1 and 3, respectively. The magnet–luminescence–structure correlations as well as relaxation pathways are investigated by ab initio calculations and fluorescent spectrometry.