期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 7, 页码 2504-2513出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b10714
关键词
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资金
- EPSRC
- Ramsay Memorial Trust
- University of Manchester
- Italian Ministry of Education, Universities and Research (MIUR)
- CNR-STFC [3420 2014-2020]
- MIUR (Italy) [HYFSRT]
- DFG [SL104/5-1, SPP1601]
Magnetic exchange interactions within the asymmetric dimetallic compounds [hqH(2)][Ln(2)(hq)(4)(NO3)(3)]center dot MeOH, (Ln = Er(III) and Yb(III), hqH = 8-hydroxyquinoline) have been directly probed with EPR spectroscopy and accurately modeled by spin Hamiltonian techniques. Exploitation of site selectivity via doping experiments in Y(III) and Lu(III) matrices yields simple EPR spectra corresponding to isolated Kramers doublets, allowing determination of the local magnetic properties of the individual sites within the dimetallic compounds. CASSCF-SO calculations and INS and far-IR measurements are all employed to further support the identification and modeling of the local electronic structure for each site. EPR spectra of the pure dimetallic compounds are highly featured and correspond to transitions within the lowest-lying exchange-coupled manifold, permitting determination of the highly anisotropic magnetic exchange between the lanthanide ions. We find a unique orientation for the exchange interaction, corresponding to a common elongated oxygen bridge for both isostructural analogs. This suggests a microscopic physical connection to the magnetic superexchange. These results are of fundamental importance for building and validating model microscopic Hamiltonians to understand the origins of magnetic interactions between lanthanides and how they may be controlled with chemistry.
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