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  Tetrairon(II) extended metal atom chains as single-molecule magnets

Nicolini, A., Affronte, M., SantaLucia, D. J., Borsari, M., Cahier, B., Caleffi, M., et al. (2021). Tetrairon(II) extended metal atom chains as single-molecule magnets. Dalton Transactions, 50(22), 7571-7589. doi:10.1039/D1DT01007G.

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 Creators:
Nicolini, Alessio1, 2, Author
Affronte, Marco2, Author
SantaLucia, Daniel J.3, Author
Borsari, Marco1, Author
Cahier, Benjamin4, Author           
Caleffi, Matteo2, Author
Ranieri, Antonio5, Author
Berry, John F.3, Author
Cornia, Andrea1, Author
Affiliations:
1Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia & INSTM, I-41125 Modena, Italy, ou_persistent22              
2Department of Physics, Informatics and Mathematics, University of Modena and Reggio Emilia, I-41125 Modena, Italy, ou_persistent22              
3Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA, ou_persistent22              
4Research Group Manganas, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541709              
5Department of Life Sciences, University of Modena and Reggio Emilia, I-41125 Modena, Italy, ou_persistent22              

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 Abstract: Iron-based extended metal atom chains (EMACs) are potentially high-spin molecules with axial magnetic anisotropy and thus candidate single-molecule magnets (SMMs). We herein compare the tetrairon(II), halide-capped complexes [Fe4(tpda)3Cl2] (1Cl) and [Fe4(tpda)3Br2] (1Br), obtained by reacting iron(II) dihalides with [Fe2(Mes)4] and N2,N6-di(pyridin-2-yl)pyridine-2,6-diamine (H2tpda) in toluene, under strictly anhydrous and anaerobic conditions (HMes = mesitylene). Detailed structural, electrochemical and Mössbauer data are presented along with direct-current (DC) and alternating-current (AC) magnetic characterizations. DC measurements revealed similar static magnetic properties for the two derivatives, with χMT at room temperature above that for independent spin carriers, but much lower at low temperature. The electronic structure of the iron(II) ions in each derivative was explored by ab initio (CASSCF-NEVPT2-SO) calculations, which showed that the main magnetic axis of all metals is directed close to the axis of the chain. The outer metals, Fe1 and Fe4, have an easy-axis magnetic anisotropy (D = −11 to −19 cm−1, |E/D| = 0.05–0.18), while the internal metals, Fe2 and Fe3, possess weaker hard-axis anisotropy (D = 8–10 cm−1, |E/D| = 0.06–0.21). These single-ion parameters were held constant in the fitting of DC magnetic data, which revealed ferromagnetic Fe1–Fe2 and Fe3–Fe4 interactions and antiferromagnetic Fe2–Fe3 coupling. The competition between super-exchange interactions and the large, noncollinear anisotropies at metal sites results in a weakly magnetic non-Kramers doublet ground state. This explains the SMM behavior displayed by both derivatives in the AC susceptibility data, with slow magnetic relaxation in 1Br being observable even in zero static field.

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Language(s): eng - English
 Dates: 2021-03-262021-05-032021-06-14
 Publication Status: Issued
 Pages: 19
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/D1DT01007G
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Title: Dalton Transactions
  Abbreviation : Dalton Trans.
Source Genre: Journal
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Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: - Volume / Issue: 50 (22) Sequence Number: - Start / End Page: 7571 - 7589 Identifier: ISSN: 1477-9226
CoNE: https://pure.mpg.de/cone/journals/resource/954925269323