Magnetic interactions in a series of homodinuclear lanthanide complexes
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 dysprosiu...
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| Main Authors: | , , , , , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
November 20, 2015
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| In: |
Inorganic chemistry
Year: 2015, Volume: 54, Issue: 23, Pages: 11247-11258 |
| ISSN: | 1520-510X |
| DOI: | 10.1021/acs.inorgchem.5b01673 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.inorgchem.5b01673
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| Author Notes: | Peter Comba, Michael Großhauser, Rüdiger Klingeler, Changhyun Koo, Yanhua Lan, Dennis Müller, Jaena Park, Annie Powell, Mark J. Riley, and Hubert Wadepohl |
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| 520 | |a 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 ([DyIII2(L)(OAc)4]+ and [NdIII2(L)(OAc)4]+) allowed us to thoroughly analyze the ligand field, and high-frequency EPR spectroscopy of the gadolinium(III) species ([GdIII2(L)(OAc)4]+) showed the importance of dipolar coupling in these systems. An extensive quantum-chemical analysis of the dysprosium(III) complex ([DyIII2(L)(OAc)4]+), involving an ab initio (CASSCF) wave function, explicit spin-orbit 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 χT versus T data, which therefore allowed us to establish a qualitative model for all relaxation pathways. | ||
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