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Article: Conjugated Polyelectrolyte-Induced Self-Assembly of Alkynylplatinum(II) 2,6-Bis(benzimidazol-2’-yl)pyridine Complexes

TitleConjugated Polyelectrolyte-Induced Self-Assembly of Alkynylplatinum(II) 2,6-Bis(benzimidazol-2’-yl)pyridine Complexes
Authors
KeywordsConjugated polyelectrolytes
Energy transfer
Metal–metal interactions
Platinum
Supramolecular chemistry
Issue Date2015
PublisherWiley - VCH Verlag GmbH & Co. KGaA.
Citation
Chemistry: A European Journal, 2015, v. 21 n. 46, p. 16434-16447 How to Cite?
AbstractWater‐soluble cationic alkynylplatinum(II) 2,6‐bis(benzimidazol‐2′‐yl)pyridine (bzimpy) complexes have been demonstrated to undergo supramolecular assembly with anionic polyelectrolytes in aqueous buffer solution. Metal–metal‐to‐ligand charge transfer (MMLCT) absorptions and triplet MMLCT (3MMLCT) emissions have been found in UV/Vis absorption and emission spectra of the electrostatic assembly of the complexes with non‐conjugated polyelectrolytes, driven by Pt⋅⋅⋅Pt and π–π interactions among the complex molecules. Interestingly, the two‐component ensemble formed by [Pt(bzimpy‐Et){CCC6H4(CH2NMe3‐4)}]Cl2 (1) with para‐linked conjugated polyelectrolyte (CPE), PPE‐SO3−, shows significantly different photophysical properties from that of the ensemble formed by 1 with meta‐linked CPE, mPPE‐Ala. The helical conformation of mPPE‐Ala allows the formation of strong mPPE‐Ala–1 aggregates with Pt⋅⋅⋅Pt, electrostatic, and π–π interactions, as revealed by the large Stern–Volmer constant at low concentrations of 1. Together with the reasonably large Förster radius, large HOMO–LUMO gap and high triplet state energy of mPPE‐Ala to minimize both photo‐induced charge transfer (PCT) and Dexter triplet energy back‐transfer (TEBT) quenching of the emission of 1, efficient Förster resonance energy transfer (FRET) from mPPE‐Ala to aggregated 1 molecules and strong 3MMLCT emission have been found, while the less strong PPE‐SO3−–1 aggregates and probably more efficient PCT and Dexter TEBT quenching would account for the lack of 3MMLCT emission in the PPE‐SO3−–1 ensemble.
Persistent Identifierhttp://hdl.handle.net/10722/231662
ISSN
2019 Impact Factor: 4.857
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChan, K-
dc.contributor.authorChung, CYS-
dc.contributor.authorYam, VWW-
dc.date.accessioned2016-09-20T05:24:42Z-
dc.date.available2016-09-20T05:24:42Z-
dc.date.issued2015-
dc.identifier.citationChemistry: A European Journal, 2015, v. 21 n. 46, p. 16434-16447-
dc.identifier.issn0947-6539-
dc.identifier.urihttp://hdl.handle.net/10722/231662-
dc.description.abstractWater‐soluble cationic alkynylplatinum(II) 2,6‐bis(benzimidazol‐2′‐yl)pyridine (bzimpy) complexes have been demonstrated to undergo supramolecular assembly with anionic polyelectrolytes in aqueous buffer solution. Metal–metal‐to‐ligand charge transfer (MMLCT) absorptions and triplet MMLCT (3MMLCT) emissions have been found in UV/Vis absorption and emission spectra of the electrostatic assembly of the complexes with non‐conjugated polyelectrolytes, driven by Pt⋅⋅⋅Pt and π–π interactions among the complex molecules. Interestingly, the two‐component ensemble formed by [Pt(bzimpy‐Et){CCC6H4(CH2NMe3‐4)}]Cl2 (1) with para‐linked conjugated polyelectrolyte (CPE), PPE‐SO3−, shows significantly different photophysical properties from that of the ensemble formed by 1 with meta‐linked CPE, mPPE‐Ala. The helical conformation of mPPE‐Ala allows the formation of strong mPPE‐Ala–1 aggregates with Pt⋅⋅⋅Pt, electrostatic, and π–π interactions, as revealed by the large Stern–Volmer constant at low concentrations of 1. Together with the reasonably large Förster radius, large HOMO–LUMO gap and high triplet state energy of mPPE‐Ala to minimize both photo‐induced charge transfer (PCT) and Dexter triplet energy back‐transfer (TEBT) quenching of the emission of 1, efficient Förster resonance energy transfer (FRET) from mPPE‐Ala to aggregated 1 molecules and strong 3MMLCT emission have been found, while the less strong PPE‐SO3−–1 aggregates and probably more efficient PCT and Dexter TEBT quenching would account for the lack of 3MMLCT emission in the PPE‐SO3−–1 ensemble.-
dc.languageeng-
dc.publisherWiley - VCH Verlag GmbH & Co. KGaA.-
dc.relation.ispartofChemistry: A European Journal-
dc.subjectConjugated polyelectrolytes-
dc.subjectEnergy transfer-
dc.subjectMetal–metal interactions-
dc.subjectPlatinum-
dc.subjectSupramolecular chemistry-
dc.titleConjugated Polyelectrolyte-Induced Self-Assembly of Alkynylplatinum(II) 2,6-Bis(benzimidazol-2’-yl)pyridine Complexes-
dc.typeArticle-
dc.identifier.emailChung, CYS: cyschung@hku.hk-
dc.identifier.emailYam, VWW: wwyam@hku.hk-
dc.identifier.authorityChung, CYS=rp02672-
dc.identifier.authorityYam, VWW=rp00822-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.201501804-
dc.identifier.pmid26429604-
dc.identifier.scopuseid_2-s2.0-84946092256-
dc.identifier.hkuros265014-
dc.identifier.volume21-
dc.identifier.issue46-
dc.identifier.spage16434-
dc.identifier.epage16447-
dc.identifier.isiWOS:000365132100021-
dc.publisher.placeGermany-

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