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Computational Design of Strongly σ/π-Conjugated Compounds with a Start at the Omni-Conjugated [3]Radialene
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-336170OAI: oai:DiVA.org:uu-336170DiVA: diva2:1165210
Available from: 2017-12-12 Created: 2017-12-12 Last updated: 2017-12-20
In thesis
1. Hyperconjugation in Group 14 Organic Compounds: Design and Property Investigations
Open this publication in new window or tab >>Hyperconjugation in Group 14 Organic Compounds: Design and Property Investigations
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Nowadays π-conjugated molecules are widely used as materials for devices in organic and molecular electronics. This is due to the ability of such molecules to conduct electricity. However, π-conjugation leads to molecular rigidness and associated lower solubility, which limits possible applications. Meanwhile, there are other types of conjugation that do not cause molecular rigidness but still provide conductivity. One of them is so called hyperconjugation. While π-conjugation involves only p atomic orbitals, hyperconjugation is characterized by interaction of π and σ orbitals. Hyperconjugation is normally weaker than π-conjugation, thus, in order to get strongly hyperconjugated molecules they should be enhanced in some way.

In this thesis, I describe methods for design of strongly hyperconjugated molecules. It is possible to increase the strength of hyperconjugation by various methods and some of them are discussed. We performed quantum chemical calculations in order to investigate optical and geometric properties of the hyperconjugated molecules and evaluate the relative strength of hyperconjugation. In some cases, results of calculations were compared with experimental results aiming to confirm the relevance of the calculations. First, we have investigated how the change of group 14 elements in the 1,4-ditetrelocyclohexa-2,5-dienes influence the hyperconjugation strength. Next, the substituent effect was considered in fulvenes and their hyperconjugated analogs. We showed this effect from the perspective of the substituents influence on the aromatic properties of molecules in the ground and first electronically excited states. Further, the gradual shift when going from monomer to oligomers were investigated. For this hyperconjugated oligomers were constructed from 1,4-disilacyclohexa-2,5-diene and cyclobutadisilole fragments. Additionally we showed the influence of electron withdrawing and electron donating groups on hyperconjugation in siloles and 1,4-disilacyclohexa-2,5-dienes. Finally, hyperconjugation was investigated in a set of silicon-containing omni-hyperconjugated compounds.

The results obtained from this research showed that hyperconjugation strength can be increased significantly up to levels comparable to purely π-conjugated molecules. We hope that these results will be useful in development of other hyperconjugated small molecules, oligomers, and polymers, which can be further used as material for electronic devices.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. 61 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1613
Keyword
1, 4-disilacyclohexa-2, 5-diene, aromaticity, computational chemistry, conjugation, cross-hyperconjugation, hyperconjugation, group 14 elements, organosilicon chemistry, silole
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-336192 (URN)978-91-513-0190-7 (ISBN)
Public defence
2018-02-09, Häggsalen, Ångström laboratory, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2018-01-19 Created: 2017-12-12 Last updated: 2018-01-19

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