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dc.contributor.authorGuo, S-X
dc.contributor.authorXie, J
dc.contributor.authorGilbert-Wilson, R
dc.contributor.authorBirkett, SL
dc.contributor.authorBond, AM
dc.contributor.authorWedd, AG
dc.date.available2014-05-21T22:26:02Z
dc.date.issued2011-01-01
dc.identifierhttp://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000285419900008&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=d4d813f4571fa7d6246bdc0dfeca3a1c
dc.identifier.citationGuo, S. -X., Xie, J., Gilbert-Wilson, R., Birkett, S. L., Bond, A. M. & Wedd, A. G. (2011). Synthesis and redox properties of triarylmethane dye cation salts of anions [M6O19](2-) (M = Mo, W). DALTON TRANSACTIONS, 40 (2), pp.356-366. https://doi.org/10.1039/c0dt00882f.
dc.identifier.issn1477-9226
dc.identifier.urihttp://hdl.handle.net/11343/29033
dc.descriptionC1 - Journal Articles Refereed
dc.description.abstractFour salts have been isolated combining the triarylmethane dye cations pararosaniline (PR(+)) and crystal violet (CV(+)) with the hexametalates [M(6)O(19)](2-) (M = Mo, W). A new hexatungstic acid H(2)[W(6)O(19)]·4dma (dma = dimethylacetamide) was isolated and is a useful synthon for hexatungstate salts. Single-crystal X-ray diffraction confirmed the presence of PR(+) and [Mo(6)O(19)](2-) ions in [PR](2)[Mo(6)O(19)]·6dmf (dmf = dimethylformamide). A number of charge-assisted hydrogen bonds N-H···O exist between the cation -NH(2) functions and the anion oxygen atoms. Comparative cyclic voltammetry of salts [A]Cl (A = PR, CV), [Bu(4)N](2)[M(6)O(19)](2-) and A(2)[M(6)O(19)] was established in MeCN and Me(2)SO solutions and of solids in contact with the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide [emim][tfsa]. In the molecular solvents, the reversible potential for the process [Mo(6)O(19)](2-/3-) is less negative than the first reduction processes of the dye cations. In contrast, that for [W(6)O(19)](2-/3-) is more negative. Spectro-electrochemistry and bulk electrolysis experiments reveal significantly different pathways in the two cases. In contrast, in the [emim][tfsa] medium, a positive shift in reduction potential of at least 400 mV is seen for the anion processes but relatively little change for the dye cation processes. This means that initial reduction of the anions always precedes that of the dyes, providing significant simplification of the complex voltammetric data. Chemically modified electrodes can be used in the ionic liquid because of slow dissolution kinetics. However, reduced anion salts dissolve rapidly, allowing dissolved phase electrochemistry to be examined. The electrochemistries of the oxidized salts A(2)[M(6)O(19)] are essentially those of the individual ions, although low level interaction of A(+) with reduced anions [M(6)O(19)](3-,4-) is evident. The work establishes protocols for synthesis and handling of intensely absorbing and relatively insoluble salts which can now be applied to systems containing more complex polyoxometalate anions.
dc.formatapplication/pdf
dc.languageEnglish
dc.publisherROYAL SOC CHEMISTRY
dc.subjectTransition Metal Chemistry; Expanding Knowledge in the Chemical Sciences
dc.titleSynthesis and redox properties of triarylmethane dye cation salts of anions [M6O19](2-) (M = Mo, W)
dc.typeJournal Article
dc.identifier.doi10.1039/c0dt00882f
melbourne.peerreviewPeer Reviewed
melbourne.affiliationThe University of Melbourne
melbourne.affiliation.departmentChemistry
melbourne.source.titleDALTON TRANSACTIONS
melbourne.source.volume40
melbourne.source.issue2
melbourne.source.pages356-366
melbourne.publicationid160432
melbourne.elementsid332871
melbourne.contributor.authorBIRKETT, STEPHEN
melbourne.contributor.authorWedd, Anthony
melbourne.contributor.authorXIE, JINGLI
melbourne.contributor.authorGILBERT-WILSON, RYAN JAMES
dc.identifier.eissn1477-9234
melbourne.accessrightsThis item is currently not available from this repository


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