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Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers

2006-12-15Journal article Restricted access
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dc.contributor.authorCosta, Alexandra I.
dc.contributor.authorPrata, José V.
dc.date.accessioned2020-06-09T15:59:51Z
dc.date.available2020-06-09T15:59:51Z
dc.date.issued2006-12-15
dc.description.abstractThe synthesis of two 1,3‐bis(4‐ethynylbenzyloxy)calix[4]arenes, 5,11,17,23‐tetrakis(1,1‐dimethylethyl)‐25,27‐bis(4‐ethynylbenzyloxy)‐26,28‐dihydroxycalix[4]arene (1 ) and 25,27‐bis(4‐ethynylbenzyloxy)‐26,28‐dihydroxycalix[4]arene (2 ), was accomplished through Sonogashira coupling of appropriate calixarene derivatives. Methods for the polymerization of these bifunctional building blocks with Rh(I) as a catalyst, leading ultimately to conjugated polymers having calix[4]arene units incorporated into the main chain, were explored. Calixarenes 1 and 2 were efficiently polymerized with rhodium‐based initiators and afforded the conjugated polymers poly{5,11,17,23‐tetrakis(1,1‐dimethylethyl)‐25,27‐bis(4‐ethynylbenzyloxy)‐26,28‐dihydroxycalix[4]arene} (poly 1 ) and poly{25,27‐bis(4‐ethynylbenzyloxy)‐26,28‐dihydroxycalix[4]arene}. Depending on the conditions, high conversions and good yields were obtained. The effects of adding cocatalysts (NHEt2 and/or PPh3) were studied in connection with the number‐average molecular weight and the molecular weight distribution of the resultant polymer (poly 1 ) and tentatively correlated with the formation of low‐molecular‐weight materials. A catalytic system containing triphenylphosphine as the sole additive ([Rh(nbd)Cl]2; [Rh]/[PPh3] = 0.5) proved to be the best for the polymerization of p ‐tert ‐butylcalixarene compound 1 . Linear polymers having high number‐average molecular weights (up to 1.1 × 105 g mol−1) with low polydispersities were produced under these conditions. For debutylated homologue 2 , its polymerization was best carried out in the absence of any added cocatalyst. A cyclopolymerization route, comprising the intramolecular ring closing of the calix[4]arene pendant ethynyl groups followed by an intermolecular propagation step, is advanced to explain the results.pt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationCOSTA, Alexandra I.; PRATA, José V. – Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers. Journal of Polymer Science Part A: Polymer Chemistry. ISSN 0887-624X. Vol. 44, N.º 24 (2006), pp. 7054-7070pt_PT
dc.identifier.doi10.1002/pola.21797pt_PT
dc.identifier.issn0887-624X
dc.identifier.issn1099-0518
dc.identifier.urihttp://hdl.handle.net/10400.21/11810
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.publisherWileypt_PT
dc.relationIPL/21/2003 - Project of Instituto Politécnico de Lisboapt_PT
dc.relation.publisherversionhttps://onlinelibrary.wiley.com/doi/epdf/10.1002/pola.21797pt_PT
dc.subjectCalixarenept_PT
dc.subjectCatalysispt_PT
dc.subjectConjugated polymerspt_PT
dc.subjectCyclopolymerizationpt_PT
dc.subjectRhodiumpt_PT
dc.subjectSonogashira couplingpt_PT
dc.titleSynthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymerspt_PT
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage7070pt_PT
oaire.citation.issue24pt_PT
oaire.citation.startPage7054pt_PT
oaire.citation.titleJournal of Polymer Science Part A: Polymer Chemistrypt_PT
oaire.citation.volume44pt_PT
person.familyNameCosta
person.familyNamePrata
person.givenNameAlexandra
person.givenNameJosé Virgílio
person.identifier191765
person.identifier.ciencia-id4212-F7BF-D971
person.identifier.ciencia-idC11A-9130-8981
person.identifier.orcid0000-0002-5518-6506
person.identifier.orcid0000-0002-9068-2847
person.identifier.ridB-7214-2008
person.identifier.scopus-author-id8968446100
person.identifier.scopus-author-id9276778400
rcaap.rightsclosedAccesspt_PT
rcaap.typearticlept_PT
relation.isAuthorOfPublication5f3891cc-260d-41d3-b803-4fd17e3734bd
relation.isAuthorOfPublication15e229f3-a619-4931-87eb-799091dc1601
relation.isAuthorOfPublication.latestForDiscovery15e229f3-a619-4931-87eb-799091dc1601

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