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Poly(biferrocenylethynyl)arene and bis(biferrocenyl)diynyl complexes and their redox chemistry

hal.structure.identifierInstitut des Sciences Moléculaires [ISM]
dc.contributor.authorWANG, Yanlan
hal.structure.identifierInstitut des Sciences Moléculaires [ISM]
dc.contributor.authorRAPAKOUSIOU, Amalia
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorCHASTANET, Guillaume
hal.structure.identifierLaboratoire de chimie de coordination [LCC]
dc.contributor.authorSALMON, Lionel
hal.structure.identifierInstitut des Sciences Moléculaires [ISM]
dc.contributor.authorRUIZ, Jaime
hal.structure.identifierInstitut des Sciences Moléculaires [ISM]
dc.contributor.authorASTRUC, Didier
dc.date.issued2013
dc.identifier.issn0276-7333
dc.description.abstractEnOrange linear bis-, star tris-, and dendritic tetra-biferrocenes linked by rigid ethynylaryl and diynyl spacers were synthesized through Sonogashira coupling and homocoupling reactions and oxidized to robust blue biferrocenium complexes. The proximity of the two ferrocenyl units to each other in the biferrocenyl units introduces electrostatic and electronic effects that are observed by cyclic voltammetry and are responsible for mixed-valence stabilization and localization. The use of the polyfluorinated electrolyte [n-Bu4N][BAr4F] {ArF = 3,5-bis(trifluoromethyl)phenyl} allows observing considerable enhancement of these effects and separation of electrochemical waves representing the two ferrocenyl groups of the biferrocenyl unit. The electrostatic effect is also selectively observed with the latter electrolyte between the two central ferrocenyl units of bis(biferrocenyl)diyne. Oxidation of all of these poly(biferrocenyl) complexes using a ferricinium salt yields blue, robust biferrocenium complexes. Their localized mixed-valent electronic structure was demonstrated at both Mössbauer and infrared time scales even with the counteranion (BAr4F) that provokes the maximum electrostatic effect and very much enhances the difference between the two oxidation potentials. Their near-infrared spectra show the intervalent charge transfer and are similar to those previously recorded for biferrocenium and derivatives, confirming the class-II mixed valence. The biferrocene units around the arene linker are completely electronically independent in the neutral and cationic complexes. In conclusion, from a practical standpoint, the easy oxidation of these stiff electrochromic nanosystems and the largely increased robustness of their oxidized form compared to ferricinium make their potential use as electrochromes considerably more attractive than that of simple ferrocene derivatives.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.subject.enOrganic chemistry
dc.subject.enRedox
dc.subject.enComplex compounds
dc.title.enPoly(biferrocenylethynyl)arene and bis(biferrocenyl)diynyl complexes and their redox chemistry
dc.typeArticle de revue
dc.identifier.doi10.1021/om400864q
dc.subject.halChimie/Matériaux
bordeaux.journalOrganometallics
bordeaux.page6136-6146
bordeaux.volume32
bordeaux.issue20
bordeaux.peerReviewedoui
hal.identifierhal-00913476
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00913476v1
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