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Mo3Q7 (Q = S, Se) Clusters Containing Dithiolate/Diselenolate Ligands: Synthesis, Structures, and Their Use as Precursors of Magnetic Single-Component Molecular Conductors
dc.contributor.author | Gushchin, Artem L. | |
dc.contributor.author | Llusar, Rosa | |
dc.contributor.author | Vicent Barrera, Cristian | |
dc.contributor.author | Abramov, Pavel A. | |
dc.contributor.author | Gómez García, Carlos J. | |
dc.date.accessioned | 2015-01-15T12:36:53Z | |
dc.date.available | 2015-01-15T12:36:53Z | |
dc.date.issued | 2013-05 | |
dc.identifier.citation | European Journal of Inorganic Chemistry, Volume 2013, Issue 14, p. 2615–2622, May 2013 | ca_CA |
dc.identifier.issn | 1099-0682 | |
dc.identifier.uri | http://hdl.handle.net/10234/112439 | |
dc.description.abstract | The coordination chemistry of dithiolene and diselenolene ligands towards the all-selenium [Mo3Se7Br6]2– dianion has been investigated. Complexes (nBu4N)2[Zn(dmit)2] (dmit = 1,3-dithia-2-thioxo-4,5-dithiolate) and (nBu4N)2[Zn(dsit)2] (dsit = 1,3-dithia-2-thioxo-4,5-diselenolate) were employed as ligand precursors. The (nBu4N)2[Zn(dmit)2] complex in acetonitrile at reflux showed unexpected reactivity with [Mo3Se7Br6]2– dianion in which the inner Se atoms were replaced by S (all but the μ3-Se atom) to afford a series of mixed chalcogen [Mo3Se7–xSx(dmit)3]2– (x = 0–6) dianions. Reaction of the [Mo3S4Se3Br6]2– dianion with (nBu4N)2[Zn(dmit)2] under similar conditions also produced a mixed dmit-containing cluster formulated as [Mo3S7–xSex(dmit)3]2– (x = 0–3). The reactions were conveniently monitored by electrospray ionization mass spectrometry. The reactions of (nBu4N)2[Zn(dmit)2] and (nBu4N)2[Zn(dsit)2] with the [Mo3Se7Br6]2– dianion in dichloromethane at room temperature prevented chalcogen scrambling and allowed us to isolate the cluster salts (nBu4N)2[Mo3Se7(dmit)3] {(nBu4N)2[1]} and (nBu4N)2[Mo3Se7(dsit)3] {(nBu4N)2[2]} in analytically pure form. The crystallization of (nBu4N)2[1] from dichloromethane/diethyl ether resulted in (nBu4N)2[Mo3Se6.1S0.9(dmit)3] with partial substitution of the Seeq atoms in the cluster core. The crystal structure of (nBu4N)2[Mo3Se6.1S0.9(dmit)3] was determined by single-crystal X-ray analysis. Dianionic complexes (nBu4N)2[1], (nBu4N)2[2], and (nBu4N)2[Mo3Se7–xSx(dmit)3] (x = 0–6) were partially oxidized by iodine to afford dark semiconducting powders. These solids exhibit moderate electrical conductivities (7 × 10–2 to 6 × 10–3 S cm–1) and present antiferromagnetic exchange interactions and therefore represent new examples of magnetic Mo3Q7-based single-component conductors. | ca_CA |
dc.format.extent | 8 p. | ca_CA |
dc.format.mimetype | application/pdf | ca_CA |
dc.language.iso | eng | ca_CA |
dc.publisher | WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim | ca_CA |
dc.rights | Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim | ca_CA |
dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | * |
dc.subject | Cluster compounds | ca_CA |
dc.subject | Chalcogens | ca_CA |
dc.subject | Molybdenum | ca_CA |
dc.subject | Selenium | ca_CA |
dc.subject | Conducting materials | ca_CA |
dc.subject | Magnetic properties | ca_CA |
dc.title | Mo3Q7 (Q = S, Se) Clusters Containing Dithiolate/Diselenolate Ligands: Synthesis, Structures, and Their Use as Precursors of Magnetic Single-Component Molecular Conductors | ca_CA |
dc.type | info:eu-repo/semantics/article | ca_CA |
dc.identifier.doi | http://dx.doi.org/10.1002/ejic.201201532 | |
dc.rights.accessRights | info:eu-repo/semantics/restrictedAccess | ca_CA |
dc.relation.publisherVersion | http://onlinelibrary.wiley.com/doi/10.1002/ejic.201201532/abstract | ca_CA |
dc.type.version | info:eu-repo/semantics/publishedVersion | ca_CA |
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