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Charge Transfer Through Cross-π-conjugated and Cross-hyperconjugated Bridges: An Intervalence Charge Transfer Study
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry. (Leif Hammarström)
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry. (H. Ottosson)
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
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(English)Manuscript (preprint) (Other academic)
Keyword [en]
Intervalence charge transfer, Cross-conjugation, Cross-hyperconjugation
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-180437OAI: oai:DiVA.org:uu-180437DiVA: diva2:550376
Available from: 2012-09-07 Created: 2012-09-06 Last updated: 2012-10-01Bibliographically approved
In thesis
1. Bridge Mediated Electron Transfer in Conjugated and Cross-Conjugated Donor-Acceptor Compounds
Open this publication in new window or tab >>Bridge Mediated Electron Transfer in Conjugated and Cross-Conjugated Donor-Acceptor Compounds
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Detailed understanding of electron transfer reactions is important in many aspects of chemistry, biology and solar energy conversion.

The main aim of this thesis is to provide further insight into electron transfer through highly conjugated bridge structures. Towards this end, three series of donor-acceptor dyads have been studied, all using an oligo(1,4-phenylene-ethynylene) moiety as the bridge. A common theme in these series is that they explore the effects of having either an ethynylene or phenylene as the attachment group between the bridge and the donor or acceptor. Photophysical characterization of these dyads was carried out by means of time resolved laser spectroscopy. The results show that having an ethynylene as attachment group results in higher rates for bridge mediated electron and energy transfer compared to similar systems, where a phenylene was used.

It was also found that most of the investigated systems show a fast back electron transfer. A notable exception is a zinc(II) phthalocyanine- gold(III) porphyrin dyad, where very fast photoinduced electron transfer (kPET = 1.0×1012 s-1) was followed by relatively slow back electron transfer (kBET = 1.0×109 s-1). A complementary DFT investigation indicated that the charge shifted state involves a reduction of the gold ion, rather than the porphyrin ring. This results in lower electronic coupling between the reduced gold porphyrin and the bridge and thus slower back electron transfer.

A series of zinc porphyrin platinum acetylide dyads was used to explore the effects on electronic coupling of different attachments points on the porphyrin ring. For the investigated system it was found that linking at the meso-position results in an eight-fold increase in electron transfer rate compared to the β-position.

In addition, a series of mixed valence compounds was used to investigate electronic coupling mediated by cross-hyperconjugated or cross-π-conjugated bridges. The results indicate coupling elements of 100-400 cm-1, with the cross-π-conjugated bridge having the largest coupling. A complementary TD-DFT study indicates that both through bond and through space coupling can be active in these systems. The relative contribution of these two mechanisms to the electronic coupling is highly conformer dependent.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2012. 71 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 974
Keyword
Electron transfer, Ultrafast, Long-range, Intervalence charge transfer, cross conjugation, hyperconjugation
National Category
Physical Chemistry
Research subject
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-180442 (URN)978-91-554-8474-3 (ISBN)
Public defence
2012-10-19, Polhemssalen, Ångström lab, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
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Supervisors
Available from: 2012-10-01 Created: 2012-09-07 Last updated: 2013-01-23Bibliographically approved

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