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Influence of local microenvironment on the double hydrogen transfer in porphycene

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dc.abstract.enWe performed time-resolved transient absorption and fluorescence anisotropy measurements in orderto study tautomerization of porphycene in rigid polymer matrices at cryogenic temperatures. Studieswere carried out in poly(methyl methacrylate) (PMMA), poly(vinyl butyral) (PVB), and poly(vinyl alcohol)(PVA). The results prove that in all studied media hydrogen tunnelling plays a significant role in thedouble hydrogen transfer which becomes very sensitive to properties of the environment below approx.150 K. We also demonstrate that there exist two populations of porphycene molecules in rigid media:‘‘hydrogen-transferring’’ molecules, in which tautomerization occurs on time scales below 1 ns and‘‘frozen’’ molecules in which double hydrogen transfer is too slow to be monitored with nanosecondtechniques. The number of ‘‘frozen’’ molecules increases when the sample is cooled. We explain thiseffect by interactions of guest molecules with a rigid host matrix which disturbs symmetry of porphyceneand hinders tunnelling. Temperature dependence of the number of hydrogen-transferring moleculessuggests that the factor which restores the symmetry of the double-minimum potential well inporphycene are intermolecular vibrations localized in separated regions of the amorphous polymer
dc.affiliationUniwersytet Warszawski
dc.contributor.authorFita, Piotr
dc.contributor.authorListkowski, Arkadiusz
dc.contributor.authorGorski, Aleksander
dc.contributor.authorRadzewicz, Czesław
dc.contributor.authorKopycki, Przemysław
dc.contributor.authorKasprzycki, Piotr
dc.contributor.authorWaluk, Jacek
dc.contributor.authorJ.S.Birch, David
dc.date.accessioned2024-01-25T04:13:53Z
dc.date.available2024-01-25T04:13:53Z
dc.date.issued2020
dc.description.financePublikacja bezkosztowa
dc.description.number30
dc.description.volume22
dc.identifier.doi10.1039/D0CP02687E
dc.identifier.issn1463-9076
dc.identifier.urihttps://repozytorium.uw.edu.pl//handle/item/109256
dc.identifier.weblinkhttp://pubs.rsc.org/en/content/articlepdf/2020/CP/D0CP02687E
dc.languageeng
dc.pbn.affiliationphysical sciences
dc.relation.ispartofPhysical Chemistry Chemical Physics
dc.relation.pages17117-17128
dc.rightsClosedAccess
dc.sciencecloudnosend
dc.titleInfluence of local microenvironment on the double hydrogen transfer in porphycene
dc.typeJournalArticle
dspace.entity.typePublication