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A comparative computational investigation of the substituent effects on geometric, electronic, and optical properties of 1,4-disilacyclo-hexa-2,5- dienes and siloles
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry. (Henrik Ottosson)
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry. (Henrik Ottosson)
(English)Manuscript (preprint) (Other (popular science, discussion, etc.))
Identifiers
URN: urn:nbn:se:uu:diva-123084OAI: oai:DiVA.org:uu-123084DiVA: diva2:311804
Available from: 2010-04-23 Created: 2010-04-23 Last updated: 2010-05-12
In thesis
1. Organic Heavy Group 14 Element Compounds: A Study of Their Chemical Bonding Properties Directed Towards Applications as Molecular Wires and in Synthesis
Open this publication in new window or tab >>Organic Heavy Group 14 Element Compounds: A Study of Their Chemical Bonding Properties Directed Towards Applications as Molecular Wires and in Synthesis
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The research described herein includes synthesis, spectroscopy, and quantum chemical calculations with focus on the characteristic properties of compounds with bonds between carbon and the heavier Group 14 elements.

The chapters based on the first four papers concern σ- and σ/π-conjugated compounds, although the focus of the first paper is on ring strain of bicyclo[1.1.1]pentanes with C, Si, Ge or Sn at the bridgeheads. The relationship between calculated homodesmotic ring strain energies and through-space distances between the bridgehead atoms was evaluated, and it was found that replacing one of the methylene bridges with phospha-methyl gave both low strain and short through-space distance.

Two kinds of σ/π-interacting systems were analysed with the difference that the σ- and π-bonded segments were either allowed to rotate freely relative each other or frozen into a conformer with maximal σ/π-interaction. The freely rotating systems are star-shaped oligothiophenes linked by heavy alkane segments. Density functional theory (DFT) calculations of hole reorganization energies support the measured hole mobilites. In summary, longer central oligosilane linkages, when compared to shorter, facilitate intermolecular hole-transfer between oligothiophene units.

In 1,4-disilacyclohexa-2,5-dienes, the strength of the π- and pseudo-π interaction depends on the substituents at Si. Vapour phase UV absorption spectroscopy of 2,3,5,6-tetraethyl-1,1,4,4-tetrakis(trimethylsilyl)-1,4-disilacyclohexa-2,5-diene reveals a strong absorption at 273 nm (4.50 eV). Time-dependent DFT calculations further indicate that octastannylated 1,4-disilacyclohexa-2,5-diene has is lowest excited state at 384 nm (3.23 eV). The electronic, geometric and optical properties of substituted 1,4-disilacyclohexa-2,5-dienes were compared with those of the correspondingly substituted siloles. It was found that the lowest excitations of siloles are less tunable than those of 1,4-disilacyclohexa-2,5-dienes.

The final section concerns strongly reverse-polarised 2-amino-2-siloxysilenes formed thermally from carbamylpolysilanes, and their lack of reaction with alcohols. Instead, the carbamylsilane reacts with alcohols giving silyl ethers, leading to a new benign route for alcohol protection.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2010. 81 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 747
Keyword
Silicon, Group 14 Elements, Silenes, Conjugation, Chemical Bonding, Electronic Structure, Protecting Group Chemistry
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-123088 (URN)978-91-554-7820-9 (ISBN)
Public defence
2010-06-04, B42, Husargatan 3, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2010-05-11 Created: 2010-04-23 Last updated: 2010-05-18

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