135312 20260217205527.0 doi 10.1039/d4py00259h sideral 138631 ART-2024-138631 eng Angoy, Marta Synthesis of megadalton stereoregular ring-substituted poly(phenylacetylene)s by a rhodium(<scp>i</scp>) catalyst with a N-functionalized hemilabile phosphine ligand 2024 Access copy available to the general public Unrestricted The cationic compound [Rh(nbd){κ2P,N-Ph2P(CH2)3NMe2}][BF4] efficiently catalyzes the polymerization of a series of ring-substituted phenylacetylene derivatives, R-C6H4–C[triple bond, length as m-dash]CH with groups of different electronic and steric properties at the para (R = F, CF3, Me, Bu, tBu, OMe, OBu) and meta (R = OMe) positions to give highly stereoregular ring-substituted poly(phenylacetylene)s with a cis-transoidal configuration of very high molar mass and moderate dispersities. The polymers have been characterized by size exclusion chromatography (SEC-MALS), NMR, DSC and TGA. The polymerization of phenylacetylene and 1-ethynyl-3-methoxybenzene gives megadalton poly(phenylacetylene)s, while the polymerization of 1-ethynyl-4-methoxybenzene and 1-(tert-butyl)-4-ethynylbenzene gives ultra-high molecular weight poly(phenylacetylene)s with Mn of 1.70 × 106 and 2.72 × 106, respectively. The electronic effect of the substituent strongly influences the catalytic activity. Phenylacetylene derivatives with an electron-withdrawing substituent in para position polymerize faster than those with an electron-donating substituent. info:eu-repo/grantAgreement/ES/DGA/E42-23R info:eu-repo/grantAgreement/ES/MCIN/AEI/10.13039/501100011033 info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00 info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00 info:eu-repo/semantics/openAccess by-nc https://creativecommons.org/licenses/by-nc/4.0/deed.es 4.0 2024 POLYMER SCIENCE 32 / 94 = 0.34 2024 Q2 T2 0.842 2024 Organic Chemistry 2024 Q1 Polymers and Plastics 2024 Q1 Bioengineering 2024 Q2 Biochemistry 2024 Q2 Biomedical Engineering 2024 Q2 7.6 2024 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Jiménez, M. Victoria (orcid)0000-0002-0545-9107 Vispe, Eugenio (orcid)0000-0002-4921-4734 Pérez-Torrente, Jesús J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 15, 20 (2024), 2028-2039 POLYMER CHEMISTRY POLYMER CHEMISTRY 1759-9954 1127374 http://zaguan.unizar.es/record/135312/files/texto_completo.pdf Versión publicada 2777212 http://zaguan.unizar.es/record/135312/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:135312 articulos driver 2026-02-17-20:31:13 ARTICLE