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  Bis(pyrazolato) Bridged Diiron Complexes: Ferromagnetic Coupling in a Mixed‐Valent HS‐FeII/LS‐FeIII Dinuclear Complex

Wong, J. W. L., Hua, S.-A., Demeshko, S., Dechert, S., Ye, S., & Meyer, F. (2020). Bis(pyrazolato) Bridged Diiron Complexes: Ferromagnetic Coupling in a Mixed‐Valent HS‐FeII/LS‐FeIII Dinuclear Complex. European Journal of Inorganic Chemistry, 2020(43), 4137-4145. doi:10.1002/ejic.202000697.

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 Creators:
Wong, Joanne W. L.1, Author
Hua, Shao-An1, Author
Demeshko, Serhiy1, Author
Dechert, Sebastian1, Author
Ye, Shengfa2, Author           
Meyer, Franc1, Author
Affiliations:
1Institut für Anorganische Chemie, Georg‐August‐Universität Göttingen, Tammannstrasse 4, 37077 Göttingen, Germany, ou_persistent22              
2Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              

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Free keywords: Dinuclear complexes; Mixed-valent complexes; Iron; Magnetic properties; Mössbauer spectroscopy
 Abstract: Using a new bis(tridentate) compartmental pyrazolate‐centered ligand HL, the bis(pyrazolato)‐bridged diiron complex [L2FeII2][OTf]2 (1) and its singly oxidized mixed‐valent congener [L2FeIIFeIII][OTf]3 (2) have been synthesized and structurally characterized. While 1 features two HS‐FeII ions coordinated to two cis‐axial pyridine moieties in a highly distorted octahedral environment, the metal ions in 2 are coordinated by the ligand strand in a trans‐axial configuration. Very different Fe–N bond lengths and distinctly different coordination polyhedra are associated with pronounced valence localization in the case of 2. The electronic structures and magnetic properties of 1 and 2 have been further investigated by Mössbauer spectroscopy and variable temperature magnetic susceptibility measurements. In the case of 1, weak antiferromagnetic coupling is observed between the two HS‐FeII ions (J = –0.6 cm–1), while the HS‐FeII and LS‐FeIII ions in 2 are ferromagnetically coupled (J = +5.2 cm–1) to give an ST = 5/2 ground state with significant zero‐field splitting (DFe(II) = 2.3 cm–1). The findings are rationalized with the help of DFT computations.

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Language(s): eng - English
 Dates: 2020-07-232020-10-072020-11-22
 Publication Status: Issued
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/ejic.202000697
 Degree: -

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Title: European Journal of Inorganic Chemistry
  Abbreviation : Eur. J. Inorg. Chem.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : Wiley-VCH
Pages: - Volume / Issue: 2020 (43) Sequence Number: - Start / End Page: 4137 - 4145 Identifier: ISSN: 1434-1948
CoNE: https://pure.mpg.de/cone/journals/resource/954926953810_1