Bernot Kevin, Bogani Lapo, Caneschi Andrea, Gatteschi Dante, Sessoli Roberta
La.M.M., Department of Chemistry and INSTM Research Unit, Università di Firenze, Via della Lastruccia 3, 50019, Sesto Fiorentino (FI), Italy.
J Am Chem Soc. 2006 Jun 21;128(24):7947-56. doi: 10.1021/ja061101l.
The first family of rare-earth-based single chain magnets is presented. Compounds of general formula [M(hfac)3(NITPhOPh)], where M = Eu, Gd, Tb, Dy, Ho, Er, or Yb, and PhOPh is the nitronyl-nitroxide radical (2,4'-benzoxo-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), have been structurally characterized and found to be isostructural. The characterization of both static and dynamic magnetic properties of the whole family is reported. Dy, Tb, and Ho compounds display slow relaxation of the magnetization, and ac susceptibility shows a thermally activated regime with energy barriers of 69, 45, and 34 K for Dy, Tb, and Ho compounds, respectively, while only a frequency-dependent susceptibility is observed for Er below 2.0 K. In Gd and Yb derivatives, antiferromagnetic interactions dominate. The pre-exponential factors differ by about 4 orders of magnitude. Finite size effects, due to naturally occurring defects, affect the static and dynamic properties of the compounds differently.
首次报道了基于稀土的单链磁体家族。通式为[M(hfac)3(NITPhOPh)]的化合物(其中M = Eu、Gd、Tb、Dy、Ho、Er或Yb,PhOPh为硝酰基-氮氧化物自由基(2,4'-苯并氧基-4,4,5,5-四甲基咪唑啉-1-氧基-3-氧化物))已通过结构表征,发现它们具有同构结构。报道了整个家族的静态和动态磁性能表征。Dy、Tb和Ho化合物表现出磁化强度的缓慢弛豫,交流磁化率显示出热激活机制,Dy、Tb和Ho化合物的能垒分别为69 K、45 K和34 K,而在2.0 K以下,Er仅观察到频率依赖的磁化率。在Gd和Yb衍生物中,反铁磁相互作用占主导。预指数因子相差约4个数量级。由于天然存在的缺陷导致的有限尺寸效应,对化合物的静态和动态性能产生不同的影响。