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Their one\u2010electron oxidation potentials are determined by differential pulse voltammetry (DPV) in methanol, acetonitrile, dichloromethane, and dimethyl sulfoxide. The dendrimers are more difficult to oxidize than<\/jats:italic> N<jats:italic>,<\/jats:italic>N<jats:italic>,<\/jats:italic>N<jats:italic>\u2032,<\/jats:italic>N<jats:italic>\u2032\u2010tetramethyl\u2010<\/jats:italic>p<jats:italic>\u2010phenylenediamine (TMePD). The oxidation potentials decrease with increasing dendrimer generation up to G0.5, after which the potential is essentially constant up to G2.0. The structures of both the neutral species and the radical cations are studied by DFT calculations at the B3LYP\/6\u201031G(d,p) level of theory, which include a series of simple PDs for comparison. The data show that the structural arrangement close to the PD core is similar to that of<\/jats:italic> N<jats:italic>,<\/jats:italic>N<jats:italic>,<\/jats:italic>N<jats:italic>\u2032,<\/jats:italic>N<jats:italic>\u2032\u2010tetra\u2010<\/jats:italic>n<jats:italic>\u2010alkyl\u2010<\/jats:italic>p<jats:italic>\u2010phenylenediamines, including a planar arrangement of the atoms linked to the two PD nitrogen atoms. Thus, the effect of chain size on the oxidation potential appears to be caused primarily by a simple electronic effect. The calculations indicate considerable reorientation of the dendrimer side chains on oxidation, presumably caused by interactions between the positive charge centered at the core and the neighboring ester or amide dipoles. The relative ease of oxidation of TMePD and the lowest members of the series of the dendrimers can be reproduced theoretically only when solvation was included in the calculations. The DPV peak heights vary approximately as predicted from the Stokes\u2013Einstein\u2013Sutherland equation, but the variation of the relative effective radii with the size of the dendrimer is much larger than predicted from the radii obtained by the DFT calculations, that is, the dendrimers exist in solution mainly as aggregates.<\/jats:italic><\/jats:p>","DOI":"10.1002\/cphc.200900233","type":"journal-article","created":{"date-parts":[[2009,7,18]],"date-time":"2009-07-18T01:59:01Z","timestamp":1247882341000},"page":"1805-1824","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Electrochemical One\u2010Electron Oxidation of Low\u2010Generation Polyamidoamine\u2010Type Dendrimers with a 1,4\u2010Phenylenediamine Core"],"prefix":"10.1002","volume":"10","author":[{"given":"Ole","family":"Hammerich","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Thomas","family":"Hansen","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Asbj\u00f8rn","family":"Thorvildsen","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"J\u00f8rn B.","family":"Christensen","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2009,7,24]]},"reference":[{"volume-title":"Dendrimers and Other Dendritic Polymers","year":"2001","author":"Tomalia J. 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