A Mössbauer study of the three spin states of the reduced selenium-substituted 2[4Fe-4Se]+ ferredoxin from Clostridium pasteurianum was carried out at T = 1.6 K, in perpendicular and parallel applied magnetic fields of up to 10 T. In low (0.1 T) applied fields, the spectra of the classical S = 1/2 state exhibit magnetic hyperfine patterns arising from two pairs of iron atoms with opposite hyperfine fields. The S = 7/2 state is in the slow relaxation limit at T less than or equal to 4 K in the absence of applied field. The corresponding Mössbauer spectrum can be understood in terms of anti-parallel coupling between one high-spin Fe3+ ion (Hhf = +21.2 T) and three high-spin Fe2+ ions (Hhf,xy = -25.5 T, Hhf,z = -28.5 T). For the S = 3/2 spin state, the use of high (8-10 T) applied fields was necessary to ensure the validity of the high-field approximation and overcome the intercluster spin-spin interaction. The spectral data obtained under such conditions allowed the determination of the hyperfine field (-4.2 T) and a tentative estimation of the zero-field splitting (D approximately less than 3 cm-1).

The electron paramagnetic resonance (EPR) spectra of the reduced selenium-substituted 2-[4Fe-4Se]+ ferredoxins from three bacteria of the Clostridium genus display low-field signals at g = 5.17, g = 10.11, and g = 12.76. The positions, shapes, and temperature dependencies of these signals have allowed their assignments to the three excited states of an S = 7/2 spin multiplet, the fundamental state of which is observed as unusual features in low-temperature (T less than or equal to 20 K) Mössbauer spectra. The S = 7/2 spin state is present in 2[4Fe-4Se]+ clostridial ferredoxins together with the classical S = 1/2 state and with a S = 3/2 state, the fundamental doublet of which is observed as a broad signal in the g = 3-4 region. The relative intensities of the EPR signals corresponding to these spin states depend on the species of Clostridium that the ferredoxin is extracted from. In contrast with clostridial ferredoxins, the reduced selenium-substituted ferredoxin from Bacillus stearothermophilus, which differs significantly from the clostridial proteins by its primary structure and by its containing only one tetranuclear cluster, displays only the S = 1/2 state. Thus, the high-multiplicity spin states arise from a specific interaction between the clostridial ferredoxin polypeptide chain and the reduced [4Fe-4Se]+ clusters.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCorrelation among the structural, electronic and magnetic properties of [Fe4(.mu.3-S)3(.mu.3-S2)Cp4]n+ (n = 0-2) clusters at various oxidation statesN. Dupre, P. Auric, H. M. J. Hendriks, and J. JordanovCite this: Inorg. Chem. 1986, 25, 9, 1391–1396Publication Date (Print):April 1, 1986Publication History Published online1 May 2002Published inissue 1 April 1986https://doi.org/10.1021/ic00229a020RIGHTS & PERMISSIONSArticle Views51Altmetric-Citations14LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (755 KB) Get e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

AbstractThe series of title complexes is examined by means of Mößbauer and NMR spectra together with an X‐ray structure analysis of the dication (I) (space group Pbca with Z=8).

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and structural characterization of [Fe4(.mu.3-S)3(.mu.3-S2)Cp4][MoOCl4(THF)]. A new iron-sulfur cluster with different modes of coordination at the iron sitesN. Dupre, H. M. J. Hendriks, J. Jordanov, J. Gaillard, and P. AuricCite this: Organometallics 1984, 3, 5, 800–802Publication Date (Print):May 1, 1984Publication History Published online1 May 2002Published inissue 1 May 1984https://pubs.acs.org/doi/10.1021/om00083a026https://doi.org/10.1021/om00083a026research-articleACS PublicationsRequest reuse permissionsArticle Views77Altmetric-Citations24LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

The electronic and magnetic properties of the selenium-substituted 2[4Fe-4Se]2+/+ ferredoxin (Fd) from Clostridium pasteurianum have been investigated by EPR and Mössbauer spectroscopy. The [4Fe-4Se]2+ clusters of oxidized Fd are diamagnetic and the Mössbauer spectra are nearly identical to those of oxidized 2[4Fe-4S]2+ Fd. The addition of 2e- per molecule of Se-substituted Fd causes the simultaneous appearance of three EPR signals: one (g1,2,3 = 2.103, 1.940, 1.888) is reminiscent of [4Fe-4S]+ EPR spectra and accounts for 0.7 to 0.8 spin/molecule. The two others consist of a broad signal with g = 4.5, 3.5, and approximately 2 (0.7 to 0.8 spin/molecule) and of a narrow peak at g = 5.172 which is observed up to 60 K. Peculiar features are also present in the Mössbauer spectra of 2[4Fe-4Se]+ Fd below 20 K: a subcomponent with lines near to +/- 4 mm/s and accounting for 20% of the total iron corresponds to two antiferromagnetically coupled sites in approximately a 3:1 ratio and displays fully developed paramagnetic hyperfine interactions at 4.2 K without any applied field. At 77 K, however, the reduced Se-substituted Fd yields a Mössbauer spectrum similar to that of 2[4Fe-4S]+ Fd. The new EPR and Mössbauer spectroscopic features of the 2[4Fe-4Se]+ Fd are attributed to S = 3/2 and S = 7/2 spin states which accompany the classical S = 1/2 state of [4Fe-4X]+ (X = S, Se) structures.