Magnetic interactions in a series of homodinuclear lanthanide complexes

• Verfasst von: Comba, Peter [VerfasserIn]
• Verfasst von: Großhauser, Michael [VerfasserIn]
• Verfasst von: Klingeler, Rüdiger [VerfasserIn]
• Verfasst von: Koo, Changhyun [VerfasserIn]
• Verfasst von: Lan, Yanhua [VerfasserIn]
• Verfasst von: Müller, Dennis [VerfasserIn]
• Verfasst von: Park, Jaena [VerfasserIn]
• Verfasst von: Powell, Annie [VerfasserIn]
• Verfasst von: Riley, Mark J. [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Titel: Magnetic interactions in a series of homodinuclear lanthanide complexes
• Verf.angabe: Peter Comba, Michael Großhauser, Rüdiger Klingeler, Changhyun Koo, Yanhua Lan, Dennis Müller, Jaena Park, Annie Powell, Mark J. Riley, and Hubert Wadepohl
• E-Jahr: 2015
• Jahr: November 20, 2015
• Umfang: 11 S.
• Fussnoten: Gesehen am 02.12.2020
• Titel Quelle: Enthalten in: Inorganic chemistry
• Ort Quelle: Washington, DC : American Chemical Society, 1962
• Jahr Quelle: 2015
• Band/Heft Quelle: 54(2015), 23, Seite 11247-11258
• ISSN Quelle: 1520-510X
• DOI: doi:10.1021/acs.inorgchem.5b01673
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1741684358

Abstract

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.