Rare earth stibolyl and bismolyl sandwich complexes

Noah Schwarz, Florian Bruder, Valentin Bayer, Eufemio Moreno-Pineda, Sebastian Gillhuber, Xiaofei Sun, Joris Slageren (), Florian Weigend () and Peter W. Roesky ()
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Noah Schwarz: Karlsruhe Institute of Technology Kaiserstrasse 12
Florian Bruder: Philipps-Universität Marburg Hans-Meerwein-Straße 4
Valentin Bayer: University of Stuttgart Pfaffenwaldring 55
Eufemio Moreno-Pineda: Depto. de Química-Física
Sebastian Gillhuber: Karlsruhe Institute of Technology Kaiserstrasse 12
Xiaofei Sun: Karlsruhe Institute of Technology Kaiserstrasse 12
Joris Slageren: University of Stuttgart Pfaffenwaldring 55
Florian Weigend: Philipps-Universität Marburg Hans-Meerwein-Straße 4
Peter W. Roesky: Karlsruhe Institute of Technology Kaiserstrasse 12

Nature Communications, 2025, vol. 16, issue 1, 1-11

Abstract: Abstract The design of molecular rare earth complexes to achieve unique magnetic and bonding properties is a growing area of research with possible applications in advanced materials and molecular magnetics. Recent efforts focus on developing ligand frameworks that can enhance magnetic characteristics. Here we show the synthesis and characterization of a class of rare earth complexes, [(η5-C4R4Sb)Ln(η8-C8H8)] and [(η5-C4R4Bi)Ln(η8-C8H8)], featuring η5-coordinated stibolyl and bismolyl ligands. The ligand aromaticity and bonding situation within these complexes are investigated by quantum chemical calculations. Magnetic studies of the ErIII analogues reveal large barriers and intriguing properties, including waist-restricted hysteresis and slow relaxation of the magnetization, making them single-molecule magnets. Comparison between the experimental barrier and CASSCF-SO calculations indicates that relaxation in all systems occurs through high-energy excited states. These findings suggest that stibolyl and bismolyl ligands can be promising candidates for achieving high-energy barriers in Er-based SMMs, offering a pathway to molecular designs with enhanced magnetic properties.

Date: 2025
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DOI: 10.1038/s41467-024-55474-6

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