Magnetic Interactions in a Series of Homodinuclear Lanthanide Complexes

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• 作者：Peter Comba ; Michael Gro脽hauser ; R眉diger Klingeler ; Changhyun Koo ; Yanhua Lan ; Dennis M眉ller ; Jaena Park ; Annie Powell ; Mark J. Riley ; Hubert Wadepohl
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：December 7, 2015
• 年：2015
• 卷：54
• 期：23
• 页码：11247-11258
• 全文大小：694K
• ISSN：1520-510X

文摘

A series of seven isostructural homodinuclear lanthanide complexes are reported. The magnetic properties (ac and dc SQUID measurements) are discussed on the basis of the X-ray structural properties which show that the two lanthanide sites are structurally different. MCD spectroscopy of the dysprosium(III) and neodymium(III) complexes ([Dy^III₂(L)(OAc)₄]⁺ and [Nd^III₂(L)(OAc)₄]⁺) allowed us to thoroughly analyze the ligand field, and high-frequency EPR spectroscopy of the gadolinium(III) species ([Gd^III₂(L)(OAc)₄]⁺) showed the importance of dipolar coupling in these systems. An extensive quantum-chemical analysis of the dysprosium(III) complex ([Dy^III₂(L)(OAc)₄]⁺), involving an ab initio (CASSCF) wave function, explicit spin鈥搊rbit coupling (RASSI-SO), and a ligand field analysis (Lines model and Stevens operators), is in full agreement with all experimental data (SQUID, HF-EPR, MCD) and specifically allowed us to accurately simulate the experimental 蠂T versus T data, which therefore allowed us to establish a qualitative model for all relaxation pathways.