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Inorg Chem. 2016 Apr 18;55(8):3738-49. doi: 10.1021/acs.inorgchem.5b02432. Epub 2016 Mar 29.

Anion Effects on Lanthanide(III) Tetrazole-1-acetate Dinuclear Complexes Showing Slow Magnetic Relaxation and Photofluorescent Emission.

Inorganic chemistry

Ying-Bing Lu, Xiao-Ming Jiang, Shui-Dong Zhu, Zi-Yi Du, Cai-Ming Liu, Yong-Rong Xie, Liang-Xian Liu

Affiliations

  1. Jiangxi Key Laboratory of Function of Materials Chemistry, College of Chemistry and Chemical Engineering, Gannan Normal University , Ganzhou 341000, People's Republic of China.
  2. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, Fujian 350002, People's Republic of China.
  3. Beijing National Laboratory for Molecular Sciences, Center for Molecular Science, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Republic of China.

PMID: 27023680 DOI: 10.1021/acs.inorgchem.5b02432

Abstract

Three types of lanthanide complexes based on the tetrazole-1-acetic acid ligand and the 2,2'-bipyridine coligand were prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analyses; the formulas of these complexes are [Ln2(1-tza)4(NO3)2(2,2'-bipy)2] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5)), [Dy2(1-tza)4Cl2(2,2'-bipy)2] (6), and [Yb2(1-tza)4(NO3)2(2,2'-bipy)2] (7) (1-tza = tetrazole-1-acetate and 2,2'-bipy = 2,2'-bipyridine). They are dinuclear complexes possessing similar structures but different lanthanide(III) ion coordination geometries because of the distinction of peripheral anions (such as NO3(-) and Cl(-)) and the effect of lanthanide contraction. The variable-temperature magnetic susceptibilities of 1-6 were measured. Both Dy(III) complexes (5 and 6) display field-induced single-molecule magnet behaviors. Ab initio calculations revealed that the Dy(III) complex 6 possesses a more anisotropic Dy(III) ion in comparison to that in 5. The room-temperature photoluminescence spectra of Sm(III) (1), Eu(III) (2), Tb(III) (4), and Dy(III) (5 and 6) complexes exhibit strong characteristic emissions in the visible region, whereas the Yb(III) (7) complex shows near-infrared (NIR) luminescence.

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