Guo, F.-S., He, M., Huang, G.-Z., Giblin, S. R., Billington, D., Heinemann, F. W., Tong, M.-L., Mansikkamäki, A., & Layfield, R. A. (2022). Discovery of a dysprosium metallocene single-molecule magnet with two high-temperature orbach processes. Inorganic Chemistry, 61(16), 6017–6025. https://doi.org/10.1021/acs.inorgchem.1c03980
Discovery of a dysprosium metallocene single-molecule magnet with two high-temperature Orbach processes
|Author:||Guo, Fu-Sheng1; He, Mian1; Huang, Guo-Zhang2;|
1Department of Chemistry, School of Life Sciences, University of Sussex, Brighton BN1 9QR, U.K.
2Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, School of Chemistry, Sun-Yat Sen University, Guangzhou 510006, P. R. China
3School of Physics and Astronomy, Cardiff University, Cardiff CF24 3AA, U.K.
4Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-University Erlangen-Nürnberg, Egerlandstrabe 1, 91058 Erlangen, Germany
5NMR Research Group, University of Oulu, P.O. Box 8000, Oulu FI-90014, Finland
|Online Access:||PDF Full Text (PDF, 2.3 MB)|
|Persistent link:|| http://urn.fi/urn:nbn:fi-fe2022102462788
American Chemical Society,
|Publish Date:|| 2022-10-24
Magnetic bistability in single-molecule magnets (SMMs) is a potential basis for new types of nanoscale information storage material. The standard model for thermally activated relaxation of the magnetization in SMMs is based on the occurrence of a single Orbach process. Here, we show that incorporating a phosphorus atom into the framework of the dysprosium metallocene [(CpiPr5)Dy(CpPEt4)]+[B(C₆F₅)₄]− (CpiPr5 is penta-isopropylcyclopentadienyl, CpPEt4 is tetraethylphospholyl) leads to the occurrence of two distinct high-temperature Orbach processes, with energy barriers of 1410(10) and 747(7) cm–1, respectively. These barriers provide experimental evidence for two different spin–phonon coupling regimes, which we explain with the aid of ab initio calculations. The strong and highly axial crystal field in this SMM also allows magnetic hysteresis to be observed up to 70 K, using a scan rate of 25 Oe s–1. In characterizing this SMM, we show that a conventional Debye model and consideration of rotational contributions to the spin–phonon interaction are insufficient to explain the observed phenomena.
|Pages:||6017 - 6025|
|Type of Publication:||
A1 Journal article – refereed
|Field of Science:||
116 Chemical sciences
114 Physical sciences
The authors thank the European Research Council (CoG Grant 646740), the EPSRC (EP/M022064/1), the NSF China (Projects 22131011 and 21821003), the National Key Research and Development Program of China (2018YFA0306001), the Pearl River Talent Plan of Guangdong (2017BT01C161), the Academy of Finland (Grant 332294), and the Kvantum Institute (University of Oulu). Computational resources were provided by CSC-IT Center for Science in Finland, the Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533). The authors thank Prof. Dr. Karsten Meyer for providing access to low-temperature X-ray diffraction facilities and the Friedrich-Alexander-University Erlangen-Nürnberg for generous financial support. They also thank the Diamond Light Source (beamline I11) and Dr. Sarah Day for collecting powder X-ray diffraction data on [B(C6F5)4].
|Academy of Finland Grant Number:||
332294 (Academy of Finland Funding decision)
© 2022 The Authors. Published by American Chemical Society.