Publicação
Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers
| Resumo: | The 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. |
|---|---|
| Autores principais: | Costa, Alexandra I. |
| Outros Autores: | Prata, José V. |
| Assunto: | Calixarene Catalysis Conjugated polymers Cyclopolymerization Rhodium Sonogashira coupling |
| Ano: | 2006 |
| País: | Portugal |
| Tipo de documento: | artigo |
| Tipo de acesso: | acesso restrito |
| Instituição associada: | Instituto Politécnico de Lisboa |
| Idioma: | inglês |
| Origem: | Repositório Científico do Instituto Politécnico de Lisboa |
| _version_ | 1868417501116760064 |
|---|---|
| author | Costa, Alexandra I. |
| author2 | Prata, José V. |
| author2_role | author |
| author_facet | Costa, Alexandra I. Prata, José V. |
| author_role | author |
| contributor_name_str_mv | RCIPL |
| country_str | PT |
| creators_json_txt | [{\"Person.name\":\"Costa, Alexandra I.\",\"Person.identifier.orcid\":\"0000-0002-5518-6506\"},{\"Person.name\":\"Prata, José V.\",\"Person.identifier.orcid\":\"0000-0002-9068-2847\"}] |
| datacite.contributors.contributor.contributorName.fl_str_mv | RCIPL |
| datacite.creators.creator.creatorName.fl_str_mv | Costa, Alexandra I. Prata, José V. |
| datacite.date.Accepted.fl_str_mv | 2006-12-15T00:00:00Z |
| datacite.date.available.fl_str_mv | 2020-06-09T15:59:51Z |
| datacite.date.embargoed.fl_str_mv | 2020-06-09T15:59:51Z |
| datacite.rights.fl_str_mv | http://purl.org/coar/access_right/c_16ec |
| datacite.subjects.subject.fl_str_mv | Calixarene Catalysis Conjugated polymers Cyclopolymerization Rhodium Sonogashira coupling |
| datacite.titles.title.fl_str_mv | Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers |
| dc.contributor.none.fl_str_mv | RCIPL |
| dc.creator.none.fl_str_mv | Costa, Alexandra I. Prata, José V. |
| dc.date.Accepted.fl_str_mv | 2006-12-15T00:00:00Z |
| dc.date.available.fl_str_mv | 2020-06-09T15:59:51Z |
| dc.date.embargoed.fl_str_mv | 2020-06-09T15:59:51Z |
| dc.format.none.fl_str_mv | application/pdf |
| dc.identifier.none.fl_str_mv | http://hdl.handle.net/10400.21/11810 |
| dc.language.none.fl_str_mv | eng |
| dc.publisher.none.fl_str_mv | Wiley |
| dc.rights.none.fl_str_mv | http://purl.org/coar/access_right/c_16ec |
| dc.subject.none.fl_str_mv | Calixarene Catalysis Conjugated polymers Cyclopolymerization Rhodium Sonogashira coupling |
| dc.title.fl_str_mv | Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers |
| dc.type.none.fl_str_mv | http://purl.org/coar/resource_type/c_6501 |
| description | The 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. |
| dirty | 0 |
| eu_rights_str_mv | restrictedAccess |
| format | article |
| fulltext.url.fl_str_mv | https://repositorio.ipl.pt/bitstreams/bc7f077f-4c8d-4847-bde5-0954548c1046/download |
| id | ripl_8a77a061ced1bc4f1e8276fd4e69cd2e |
| identifier.url.fl_str_mv | http://hdl.handle.net/10400.21/11810 |
| instacron_str | ipl |
| institution | Instituto Politécnico de Lisboa |
| instname_str | Instituto Politécnico de Lisboa |
| language | eng |
| network_acronym_str | ripl |
| network_name_str | Repositório Científico do Instituto Politécnico de Lisboa |
| oai_identifier_str | oai:repositorio.ipl.pt:10400.21/11810 |
| organization_str_mv | urn:organizationAcronym:ipl |
| person_str_mv | Costa, Alexandra I. Costa, Alexandra I. https://www.ciencia-id.pt/4212-F7BF-D971 4212-F7BF-D971 http://orcid.org/0000-0002-5518-6506 0000-0002-5518-6506 Prata, José V. Prata, José V. https://www.ciencia-id.pt/C11A-9130-8981 C11A-9130-8981 http://orcid.org/0000-0002-9068-2847 0000-0002-9068-2847 |
| publishDate | 2006 |
| publisher.none.fl_str_mv | Wiley |
| reponame_str | Repositório Científico do Instituto Politécnico de Lisboa |
| repository_id_str | urn:repositoryAcronym:ripl |
| service_str_mv | urn:repositoryAcronym:ripl |
| spelling | engWileypt_PTThe 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.application/pdfpt_PTSynthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymersPersonalCosta, Alexandra I.DSpacehttp://dspace.org/items/5f3891cc-260d-41d3-b803-4fd17e3734bdDSpacehttp://dspace.org/items/5f3891cc-260d-41d3-b803-4fd17e3734bdCostaAlexandraCiência IDhttps://www.ciencia-id.pt4212-F7BF-D971ORCIDhttp://orcid.org0000-0002-5518-6506Scopus Author IDhttps://www.scopus.com8968446100PersonalPrata, José V.DSpacehttp://dspace.org/items/15e229f3-a619-4931-87eb-799091dc1601DSpacehttp://dspace.org/items/15e229f3-a619-4931-87eb-799091dc1601PrataJosé VirgílioCiência IDhttps://www.ciencia-id.ptC11A-9130-8981ORCIDhttp://orcid.org0000-0002-9068-2847Researcher IDhttps://www.researcherid.comB-7214-2008Scopus Author IDhttps://www.scopus.com9276778400HostingInstitutionOrganizationalRCIPLe-mailmailto:rcaap@sp.ipl.ptrcaap@sp.ipl.ptISSNIsPartOf0887-624XISSNIsPartOf1099-0518DOIIsPartOf10.1002/pola.217972020-06-09T15:59:51Z2006-12-152006-12-15T00:00:00ZHandlehttp://hdl.handle.net/10400.21/11810http://purl.org/coar/access_right/c_16ecrestricted accessCalixareneCatalysisConjugated polymersCyclopolymerizationRhodiumSonogashira coupling452625 bytesliteraturehttp://purl.org/coar/resource_type/c_6501journal articlehttp://purl.org/coar/access_right/c_16ecapplication/pdffulltexthttps://repositorio.ipl.pt/bitstreams/bc7f077f-4c8d-4847-bde5-0954548c1046/downloadJournal of Polymer Science Part A: Polymer Chemistry442470547070 |
| spellingShingle | Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers Costa, Alexandra I. Calixarene Catalysis Conjugated polymers Cyclopolymerization Rhodium Sonogashira coupling |
| status | SINGLETON |
| subject.fl_str_mv | Calixarene Catalysis Conjugated polymers Cyclopolymerization Rhodium Sonogashira coupling |
| title | Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers |
| title_full | Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers |
| title_fullStr | Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers |
| title_full_unstemmed | Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers |
| title_short | Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers |
| title_sort | Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: novel conjugated, calixarene‐based polymers |
| topic | Calixarene Catalysis Conjugated polymers Cyclopolymerization Rhodium Sonogashira coupling |
| topic_facet | Calixarene Catalysis Conjugated polymers Cyclopolymerization Rhodium Sonogashira coupling |
| url | http://hdl.handle.net/10400.21/11810 |
| visible | 1 |