Charge trapping in dendrimers with a viologen skeleton and a radial redox gradient

DC FieldValueLanguage
dc.contributor.authorHeinen, S
dc.contributor.authorMeyer, W
dc.contributor.authorWalder, L
dc.date.accessioned2021-12-23T16:03:20Z-
dc.date.available2021-12-23T16:03:20Z-
dc.date.issued2001
dc.identifier.issn00220728
dc.identifier.urihttps://osnascholar.ub.uni-osnabrueck.de/handle/unios/5928-
dc.description.abstractThe synthesis of two charge trapping dendrimers (T-0 and T-1) consisting of one phenyl viologen in the core and 4 or 12 benzyl viologens in the branches and periphery is described. Their electrochemical properties are presented together with those of four closely related dendritic electron sponges (S-0, S-1, S-2, and S-3) built exclusively of benzyl viologens (3, 9, 21, and 45 subunits). The diffusion coefficients obtained from RDE experiments and the corresponding hydrodynamic radii (r(h)) reflect the linear growth of r(h) with the dendrimer generation number. Experimental r(h) values are well supported by MM+ force field calculations. Pimerization of peripheral benzyl viologen radical cations is observed in T-0 and T-1 similar to that described earlier for the electron sponge series. Pimerization increases with increasing dendrimer generation. Electrochemical evidence for charge trapping in the dendrimers T-0 and T-1 is presented. Results from cyclic voltammetry are difficult to interpret because of dendrimer adsorbate formation but spectroelectrochemical experiments indicate fast reduction and slow oxidation of the phenyl viologen core in T-0 and T-1. Slow oxidation is explained by the activation barrier of ca. 0.25 eV related to the tailored endergonic electron transfer from the core phenyl viologen to peripheral benzyl viologens. The possibility of electron transfer shunts related to excessive conformational freedom of the benzyl viologen branches is discussed. (C) 2001 Elsevier Science B.V. All rights reserved.
dc.language.isoen
dc.publisherELSEVIER SCIENCE SA
dc.relation.ispartofJOURNAL OF ELECTROANALYTICAL CHEMISTRY
dc.subjectcharge trapping
dc.subjectChemistry
dc.subjectChemistry, Analytical
dc.subjectdendrimer
dc.subjectElectrochemistry
dc.subjectMACROMOLECULES
dc.subjectMETAL-COMPLEXES
dc.subjectMOLECULAR TREES
dc.subjectredox gradient
dc.subjectspectroelectrochemistry
dc.subjectsynthesis
dc.subjectviologen
dc.titleCharge trapping in dendrimers with a viologen skeleton and a radial redox gradient
dc.typejournal article
dc.identifier.doi10.1016/S0022-0728(00)00215-1
dc.identifier.isiISI:000167254500003
dc.description.volume498
dc.description.issue1-2, SI
dc.description.startpage34
dc.description.endpage43
dc.contributor.orcid0000-0003-1330-2887
dc.contributor.researcheridH-5438-2019
dc.contributor.researcheridE-2915-2010
dc.publisher.placePO BOX 564, 1001 LAUSANNE, SWITZERLAND
dcterms.isPartOf.abbreviationJ. Electroanal. Chem.
crisitem.author.deptInstitut für Chemie neuer Materialien-
crisitem.author.deptidinstitute11-
crisitem.author.orcid0000-0002-5497-034X-
crisitem.author.parentorgFB 05 - Biologie/Chemie-
crisitem.author.grandparentorgUniversität Osnabrück-
crisitem.author.netidWaLo966-
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