Sulfur K-edge XAS and DFT calculations on [Fe4S 4]2+ clusters: Effects of H-bonding and structural distortion on covalency and spin topology

Abhishek Dey; Cara L. Roche; Marc A. Walters; Keith O. Hodgson; Britt Hedman; Edward I. Solomon

doi:10.1021/ic050981m

Sulfur K-edge XAS and DFT calculations on [Fe₄S ₄]²⁺ clusters: Effects of H-bonding and structural distortion on covalency and spin topology

Abhishek Dey, Cara L. Roche, Marc A. Walters, Keith O. Hodgson, Britt Hedman, Edward I. Solomon

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Sulfur K-edge X-ray absorption spectroscopy of a hydrogen-bonded elongated [Fe₄S₄]²⁺ cube is reported. The data show that this synthetic cube is less covalent than a normal compressed cube with no hydrogen bonding. DFT calculations reveal that the observed difference in electronic structure has significant contributions from both the cluster distortion and from hydrogen bonding. The elongated and compressed Fe ₄S₄ structures are found to have different spin topologies (i.e., orientation of the delocalized Fe₂S₂ subclusters which are antiferromagnetically coupled to each other). It is suggested that the H-bonding interaction with the counterion does not contribute to the cluster elongation. A magneto-structural correlation is developed for the Fe ₄S₄ cube that is used to identify the redoxactive Fe ₂S₂ subclusters in active sites of HiPIP and ferredoxin proteins involving these clusters.

Original language	English (US)
Pages (from-to)	8349-8354
Number of pages	6
Journal	Inorganic Chemistry
Volume	44
Issue number	23
DOIs	https://doi.org/10.1021/ic050981m
State	Published - Nov 14 2005

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic050981m

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title = "Sulfur K-edge XAS and DFT calculations on [Fe4S 4]2+ clusters: Effects of H-bonding and structural distortion on covalency and spin topology",

abstract = "Sulfur K-edge X-ray absorption spectroscopy of a hydrogen-bonded elongated [Fe4S4]2+ cube is reported. The data show that this synthetic cube is less covalent than a normal compressed cube with no hydrogen bonding. DFT calculations reveal that the observed difference in electronic structure has significant contributions from both the cluster distortion and from hydrogen bonding. The elongated and compressed Fe 4S4 structures are found to have different spin topologies (i.e., orientation of the delocalized Fe2S2 subclusters which are antiferromagnetically coupled to each other). It is suggested that the H-bonding interaction with the counterion does not contribute to the cluster elongation. A magneto-structural correlation is developed for the Fe 4S4 cube that is used to identify the redoxactive Fe 2S2 subclusters in active sites of HiPIP and ferredoxin proteins involving these clusters.",

author = "Abhishek Dey and Roche, {Cara L.} and Walters, {Marc A.} and Hodgson, {Keith O.} and Britt Hedman and Solomon, {Edward I.}",

year = "2005",

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doi = "10.1021/ic050981m",

language = "English (US)",

volume = "44",

pages = "8349--8354",

journal = "Inorganic Chemistry",

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publisher = "American Chemical Society",

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T1 - Sulfur K-edge XAS and DFT calculations on [Fe4S 4]2+ clusters

T2 - Effects of H-bonding and structural distortion on covalency and spin topology

AU - Dey, Abhishek

AU - Roche, Cara L.

AU - Walters, Marc A.

AU - Hodgson, Keith O.

AU - Hedman, Britt

AU - Solomon, Edward I.

PY - 2005/11/14

Y1 - 2005/11/14

N2 - Sulfur K-edge X-ray absorption spectroscopy of a hydrogen-bonded elongated [Fe4S4]2+ cube is reported. The data show that this synthetic cube is less covalent than a normal compressed cube with no hydrogen bonding. DFT calculations reveal that the observed difference in electronic structure has significant contributions from both the cluster distortion and from hydrogen bonding. The elongated and compressed Fe 4S4 structures are found to have different spin topologies (i.e., orientation of the delocalized Fe2S2 subclusters which are antiferromagnetically coupled to each other). It is suggested that the H-bonding interaction with the counterion does not contribute to the cluster elongation. A magneto-structural correlation is developed for the Fe 4S4 cube that is used to identify the redoxactive Fe 2S2 subclusters in active sites of HiPIP and ferredoxin proteins involving these clusters.

AB - Sulfur K-edge X-ray absorption spectroscopy of a hydrogen-bonded elongated [Fe4S4]2+ cube is reported. The data show that this synthetic cube is less covalent than a normal compressed cube with no hydrogen bonding. DFT calculations reveal that the observed difference in electronic structure has significant contributions from both the cluster distortion and from hydrogen bonding. The elongated and compressed Fe 4S4 structures are found to have different spin topologies (i.e., orientation of the delocalized Fe2S2 subclusters which are antiferromagnetically coupled to each other). It is suggested that the H-bonding interaction with the counterion does not contribute to the cluster elongation. A magneto-structural correlation is developed for the Fe 4S4 cube that is used to identify the redoxactive Fe 2S2 subclusters in active sites of HiPIP and ferredoxin proteins involving these clusters.

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ER -

Sulfur K-edge XAS and DFT calculations on [Fe₄S ₄]²⁺ clusters: Effects of H-bonding and structural distortion on covalency and spin topology

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