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Phosphorus Centers in π-conjugated Systems
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
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 [en]
phosphorus, phosphaalkene, phosphole, alkyne, π-conjugation, molecular electronics
National Category
Chemical Sciences
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-173114ISBN: 978-91-554-8368-5 (print)OAI: oai:DiVA.org:uu-173114DiVA: diva2:516739
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
List of papers
1. Incorporating Phosphaalkenes into Oligoacetylenes
Open this publication in new window or tab >>Incorporating Phosphaalkenes into Oligoacetylenes
2008 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 47, no 43, 8228-8231 p.Article in journal (Refereed) Published
Keyword
pi interactions, alkynes, cross-coupling, molecular electronics, phosphaalkenes
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-107845 (URN)10.1002/anie.200802253 (DOI)000260234600015 ()
Available from: 2009-08-31 Created: 2009-08-31 Last updated: 2017-12-13Bibliographically approved
2. C,C-Diacetylenic Phosphaalkenes as Heavy Diethynylethene Analogues
Open this publication in new window or tab >>C,C-Diacetylenic Phosphaalkenes as Heavy Diethynylethene Analogues
Show others...
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.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-127389 (URN)10.1021/jo901942u (DOI)000272462100002 ()
Available from: 2010-07-13 Created: 2010-07-13 Last updated: 2017-12-12Bibliographically approved
3. C,C-Diacetylenic phosphaalkenes in palladium-catalyzed cross-coupling reactions
Open this publication in new window or tab >>C,C-Diacetylenic phosphaalkenes in palladium-catalyzed cross-coupling reactions
2011 (English)In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 9, no 18, 6246-6255 p.Article in journal (Refereed) Published
Abstract [en]

The reactivity of bis-TMS-substituted C,C-diacetylenic phosphaalkene (A(2)PA) 1 in Sonogashira-Hagihara cross-coupling reactions has been examined. The selective and successive deprotection of the two silyl groups in 1 is enabled by the steric bulk of the Mes* group which renders the acetylene trans to Mes* more reactive and thereby facilitates selective and consecutive couplings with iodoarenes. In situ transformation of the TMS-protected acetylenes into Cu(I)acetylides is the key step in the synthetic sequence and enables the preparation of the first dimeric A(2)PA linked by a phenylene spacer. cis-trans Isomerization across the P = C bond is triggered by a tertiary amine and exclusively observed in the case of nitrophenyl-substituted A(2)PAs. The introduced aryl groups are integral parts of the entire p-system as evidenced by spectroscopic and electrochemical studies.

National Category
Biological Sciences
Identifiers
urn:nbn:se:uu:diva-158613 (URN)10.1039/c1ob05705g (DOI)000294263900011 ()
Available from: 2011-09-12 Created: 2011-09-12 Last updated: 2017-12-08Bibliographically approved
4. Improved Synthesis and Structural Characterization of C-Monoacetylenic Phosphaalkenes
Open this publication in new window or tab >>Improved Synthesis and Structural Characterization of C-Monoacetylenic Phosphaalkenes
(English)Manuscript (preprint) (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-173038 (URN)
Available from: 2012-04-18 Created: 2012-04-18 Last updated: 2012-08-01
5. Phosphorus Centers of Different Hybridization in Phosphaalkene-substituted Phospholes
Open this publication in new window or tab >>Phosphorus Centers of Different Hybridization in Phosphaalkene-substituted Phospholes
Show others...
2014 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 20, no 27, 8421-8432 p.Article in journal (Refereed) Published
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-173035 (URN)10.1002/chem.201402406 (DOI)000338019300028 ()
Available from: 2012-04-18 Created: 2012-04-18 Last updated: 2017-12-07Bibliographically approved

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