Significant Enhancement of Energy Barriers in Dinuclear Dysprosium Single-Molecule Magnets Through Electron-Withdrawing Effects
- 10 September 2013
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 135 (36), 13242-13245
- https://doi.org/10.1021/ja404846s
Abstract
The effect of electron-withdrawing ligands on the energy barriers of Single-Molecule Magnets (SMMs) is investigated. By introducing highly electron-withdrawing atoms on targeted ligands, the energy barrier was significantly enhanced. The structural and magnetic properties of five novel SMMs based on a dinuclear {Dy-2} phenoxo-bridged motif are explored and compared with a previously studied {Dy-2} SMM (1). All complexes share the formula [Dy-2(valdien)(2)(L)(2)]center dot solvent, where H-2 valdien = N1,N3-bis(3-methoxysalicylidene) diethylenetriamine, the terminal ligand L = NO3- (1), CH3COO- (2), ClCH2COO- ( 3), Cl2CHCOO- (4), CH3COCHCOCH3- (5), CF3COCHCOCF3- (6), and solvent = 0.5 MeOH (4), 2 CH2Cl2 (5). Systematic increase of the barrier was observed for all complexes with the most drastic increase seen in 6 when the acac ligand of 5 was fluorinated resulting in a 7-fold enhancement of the anisotropic barrier. Ab initio calculations reveal more axial g tensors as well as higher energy first excited Kramers doublets in 4 and 6 leading to higher energy barriers for those complexes.This publication has 33 references indexed in Scilit:
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