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C,C-Diacetylenic Phosphaalkenes as Heavy Diethynylethene Analogues
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science.
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2009 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 74, no 24, 9265-9273 p.Article in journal (Refereed) Published
Abstract [en]

A series of C,C-diacetylenic phosphaalkenes 1b-e has been prepared from 1-chloropenta-1,2-dien-4-ynes 6b-e in a reaction with Mes*PCl2 (Mes* = 2,4,6-(Bu-1)(3)Ph) in the presence of LDA. Under identical conditions, isomeric butadiyne-substituted phosphaalkenes 2e-f can be obtained from 3-chloropenta-1,4-diyiies 5c-f. The title compounds represent rare examples of diethynylethenes in which a constituting methylene has been replaced by a phosphorus center. The formation of both isomers can be rationalized by a common pathway that involves isomeric allenyllithium species. Spectroscopic, electrochemical, and theoretical investigations show that the phosphorus heteroatoms are an intrinsic part of the compounds' pi-systems and lead to decreased HOMO-LUMO gaps compared to those in all-carbon-based reference compounds.

Place, publisher, year, edition, pages
2009. Vol. 74, no 24, 9265-9273 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-127389DOI: 10.1021/jo901942uISI: 000272462100002OAI: oai:DiVA.org:uu-127389DiVA: diva2:329788
Available from: 2010-07-13 Created: 2010-07-13 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Phosphorus Centers in π-conjugated Systems
Open this publication in new window or tab >>Phosphorus Centers in π-conjugated Systems
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Single-molecular electronics and organic material electronics are expanding research fields that ultimately aim for a vast variety of different applications, ranging from organic light-emitting diodes, to novel ways to improve the performance and decrease the size of electronics components. To achieve these goals, research has to be focused both on the development of functional molecules, but also on device fabrication. The work of this thesis is focused on the development of synthetic routes towards novel molecules for potential organic electronics applications, together with an investigation of their optical and electronic properties.

The first part of the thesis describes the synthesis of butadiyne-substituted and diacetylenic phosphaalkenes. Theoretical, spectroscopic and electrochemical techniques have been used to understand key steps during their synthesis, and to gain further information on the conjugative properties of their π-systems. A mechanism is proposed for the formation of the butadiyne-substituted and diacetylenic phosphaalkenes and it is shown that the phosphorus heteroatom is an intrinsic part of the π-conjugated system. The incorporation of the phosphorus heteroatom leads to decreased HOMO-LUMO gaps compared to all-carbon based reference compounds.

In the second part of the thesis, acetylenic phosphaalkenes are utilized for the preparation of phosphaalkene-substituted phospholes. A first step towards the exploration of the difference in reactivity of the σ2, λ3 phosphaalkene-P and the σ3, λ3 phosphole-P is presented as the oxidation of the compounds by sulfur proceeds selectively at the σ3, λ3–P. Spectroscopic and electrochemical investigations show that the phosphaalkene is an integral part of the compounds’ π-systems, and induces a HOMO-LUMO gap decrease compared to reference compounds that lack the P=C substituent.

The third part of this thesis presents an exploratory study concerning the suitability of metathesis reactions for the assembly of alkene-bridged phosphaalkenes.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2012. 93 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 932
Keyword
phosphorus, phosphaalkene, phosphole, alkyne, π-conjugation, molecular electronics
National Category
Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:uu:diva-173114 (URN)978-91-554-8368-5 (ISBN)
Public defence
2012-06-08, Å2001, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2012-05-15 Created: 2012-04-18 Last updated: 2012-08-01Bibliographically approved

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