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High symmetry or low symmetry, that is the question – high performance Dy(iii) single-ion magnets by electrostatic potential design

A series of mononuclear lanthanide Zn–Dy–Zn type single-molecule magnets (SMMs) were synthesized and magnetically characterized. The four molecules ([Zn(2)(L(1))(2)DyCl(3)]·2H(2)O (1), [Zn(2)(L(1))(2)Dy(MeOH)Br(3)]·3H(2)O (2), [Zn(2)(L(1))(2)Dy(H(2)O)Br(2)]·[ZnBr(4)](0.5) (3) and [Zn(2)(L(2))(2)DyCl...

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Detalles Bibliográficos
Autores principales: Sun, Wen-Bin, Yan, Peng-Fei, Jiang, Shang-Da, Wang, Bing-Wu, Zhang, Yi-Quan, Li, Hong-Feng, Chen, Peng, Wang, Zhe-Ming, Gao, Song
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5523121/
https://www.ncbi.nlm.nih.gov/pubmed/28791111
http://dx.doi.org/10.1039/c5sc02986d
Descripción
Sumario:A series of mononuclear lanthanide Zn–Dy–Zn type single-molecule magnets (SMMs) were synthesized and magnetically characterized. The four molecules ([Zn(2)(L(1))(2)DyCl(3)]·2H(2)O (1), [Zn(2)(L(1))(2)Dy(MeOH)Br(3)]·3H(2)O (2), [Zn(2)(L(1))(2)Dy(H(2)O)Br(2)]·[ZnBr(4)](0.5) (3) and [Zn(2)(L(2))(2)DyCl(3)]·2H(2)O (4)) all display remarkable magnetic relaxation behavior with a relatively high energy barrier and hysteresis temperature, despite possessing a low local geometry symmetry of the center Dy(iii) ions. Ab initio studies revealed that the symmetry of the charge distribution around the Dy(iii) ion is the key factor to determine the relaxation of the SMMs. The four complexes orient their magnetic easy axes along the negative charge-dense direction of the first coordination sphere. The entire molecular magnetic anisotropy was therefore controlled by a single substituent atom in the hard plane which consists of five coordination atoms (perpendicular to the easy axis), and the lower charge distribution on this hard plane in combination with the nearly coplanarity of the five coordination atoms ultimately lead to the prominent magnetic slow relaxation. This offers an efficient and rational method to improve the dynamic magnetic relaxation of the mononuclear lanthanide SMMs that usually possess a low local geometry symmetry around the lanthanide(iii) center.