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Mavragani, N., Kitos, A. A., Mansikkamäki, A., & Murugesu, M. (2023). New members of radical bridged Ln 2 metallocene single-molecule magnets based on the unsubstituted 1,2,4,5-tetrazine ligand. Inorganic Chemistry Frontiers, 10(1), 259–266. https://doi.org/10.1039/D2QI02164A

New members of radical bridged Ln₂ metallocene single-molecule magnets based on the unsubstituted 1,2,4,5-tetrazine ligand

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Author: Mavragani, Niki1; Kitos, Alexandros A.1; Mansikkamäki, Akseli2;
Organizations: 1Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON K1N 6N5, Canada
2NMR Research Unit, University of Oulu, P.O. Box 300, 90014 Oulu, Finland
Format: article
Version: accepted version
Access: embargoed
Persistent link: http://urn.fi/urn:nbn:fi-fe202301276206
Language: English
Published: Royal Society of Chemistry, 2023
Publish Date: 2023-11-22
Description:

Abstract

Magnetic coupling plays a critical role in the overall magnetic behaviour of a single-molecule magnet (SMM). Through a careful design strategy that employs the highly delocalized 1,2,4,5-tetrazinyl (tz) radical anion with lanthanide metallocenes, a new family of dinuclear complexes was isolated; [(Cp*₂LnIII)₂(tz˙−)(THF)₂](BPh₄), (Ln = Gd (1), Tb (2), Dy (3); THF = tetrahydrofuran; Cp* = pentamethylcyclopentadienyl). The strong magnetic exchange coupling of JGd–rad = −7.2 cm−1 observed in 1, was probed through SQUID magnetometry as well as computational studies. This, combined with the highly anisotropic TbIII and DyIII ions in 2 and 3, respectively, leads to zero-field SMM behaviour and slow relaxation of the magnetization through thermally activated processes. These dinuclear complexes serve as ideal models for understanding the magnetic interactions between 4f elements

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Series: Inorganic chemistry frontiers
ISSN: 2052-1545
ISSN-E: 2052-1553
ISSN-L: 2052-1545
Volume: 10
Issue: 1
Pages: 259 - 266
DOI: 10.1039/d2qi02164a
OADOI: https://oadoi.org/10.1039/d2qi02164a
Type of Publication: A1 Journal article – refereed
Field of Science: 116 Chemical sciences
114 Physical sciences
Subjects:
Article
Funding: The authors thank the University of Ottawa, the Canada Foundation for Innovation (CFI) and Natural Sciences and Engineering Research Council of Canada (NSERC) for the financial support of this work. N. M. acknowledges the University of Ottawa and the Stavros Niarchos Foundation for financial support through scholarships. A. M. acknowledges funding provided by the Academy of Finland (grant no. 332294) and the University of Oulu (Kvantum Institute). Computational resources were provided by CSC-IT Center for Science in Finland and the Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533).
Academy of Finland Grant Number: 332294
Detailed Information: 332294 (Academy of Finland Funding decision)
Dataset Reference: Electronic supplementary information (ESI) available: Synthetic procedures, single-crystal X-ray diffraction data, additional magnetic and computational data. CCDC 2202463–2202465. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d2qi02164a
  http://dx.doi.org/10.1039/d2qi02164a
Copyright information: © 2023 The Royal Society of Chemistry. The final authenticated version is available online at https://doi.org/10.1039/D2QI02164A.