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Low-Coordinate Organopnictogens: Synthesis and Optoelectronic properties
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis work is based on the development of novel organopnictogen compounds and the exploration of their potential applications in organic electronics. In particular, incorporation of phosphorus and arsenic into π-conjugated systems is known to modify the optoelectronic properties.

The first chapter of this thesis is fully devoted to the development of a metal-free synthetic route that allows direct, sequential and stereoselective alkynylation of C,C-dibromophosphaalkenes. The subsequent unusual reactivity of thus synthesized C-mono and C,C-diacetylenicphosphaalkenes with terminal acetylenes afforded highly substituted 1-phoshpha-1,3-butadienes heavier analogue of all carbon 1,3-butadiene motifs. Optimization of the reaction condition favored exclusively the formation of 1-phospha-1,3-butadienes. Unveiling the unique cyclization of the 3-yne 1-phospha-1,3-butadiene gave highly substituted phosphole derivatives. Further, it has been experimentally shown that the P=C unit is essential for this rare cyclization and rearrangement to give π-conjugated phosphole derivatives.

The second chapter of this thesis work deals with incorporation of P/As in the form of phosphinidene and or arsinidene units as an exocyclic substituent at the bridge of the fused rigid cyclpentadithiophenes (p-CPDT) core. Furthermore, it demonstrates how this chemical modification at the bridgehead position selectively lowers the LUMO level. At a later stage, substitutions at α and α` positions of the central CPDT core was used to modify the HOMO level without further affecting the LUMO level. We also performed DFT calculations on these phosphinide/arsinidene p-CPDT derivatives to theoretical evaluate the impact of P and or As incorporation. The phosphinidene/arsinidene p-CPDT derivatives were fully characterized using electrochemical and optical spectroscopic techniques including transient absorption spectroscopy. Additionally, the arsinidene-p-CPDT were electrochemically polymerized, and the resultant polymer film was characterized by means of SEM and EDX.

The last chapter of this research work is dealing with the exploration and functionalization of open-ended small fragments of fullerene-C60 such as sumanene and truxene. Functionalisation of these motifs was achieved via the introduction of pnictogens (P/As), either in the form of phosphinidene/arsinidene or as heteroles. The optoelectronic spectra of the unprecedented pnictinidenotruxene exhibited significantly redshift absorption and three fully reversible reduction events upon electrochemical reduction.

Place, publisher, year, edition, pages
Uppsala University: Acta Universitatis Upsaliensis, 2019. , p. 128
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1766
Keywords [en]
Pnictogen, phosphorus, arsenic, phosphaalkenes, arsaalkenes, phospholes, arsoles, alkynes, π-conjugation, PAHs, Fullerene-C60, sumanene, truxene, organic electronics
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:uu:diva-373906ISBN: 978-91-513-0558-5 (print)OAI: oai:DiVA.org:uu-373906DiVA, id: diva2:1279686
Public defence
2019-03-08, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:00 (English)
Opponent
Supervisors
Available from: 2019-02-13 Created: 2019-01-17 Last updated: 2019-02-18
List of papers
1. Direct, Sequential, and Stereoselective Alkynylation of C,C-Dibromophosphaalkenes
Open this publication in new window or tab >>Direct, Sequential, and Stereoselective Alkynylation of C,C-Dibromophosphaalkenes
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2016 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 22, no 30, p. 10614-10619Article in journal (Refereed) Published
Abstract [en]

The first direct alkynylation of C,C-dibromophosphaalkenes by a reaction with sulfonylacetylenes is reported. Alkynylation proceeds selectively in the trans position relative to the P substituent to afford bromoethynylphosphaalkenes. Owing to the absence of transition metals in the procedure, the previously observed conversion of dibromophosphaalkenes into phosphaalkynes through the phosphorus analog of the Fritsch-Buttenberg-Wiechell rearrangement is thus suppressed. The bromoethynylphosphaalkenes can subsequently be converted to C,C-diacetylenic, cross-conjugated phosphaalkenes by following a Sonogashira coupling protocol in good overall yields. By using the newly described method, full control over the stereochemistry at the P=C double bond is achieved. The substrate scope of this reaction is demonstrated for different dibromophosphaalkenes as well as different sulfonylacetylenes.

Keywords
alkynylation, cross-conjugation, phosphaalkenes, Sonogashira coupling, sulfonyl coupling
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-302705 (URN)10.1002/chem.201601955 (DOI)000380273300043 ()27310813 (PubMedID)
External cooperation:
Funder
Swedish Research CouncilCarl Tryggers foundation
Available from: 2016-09-08 Created: 2016-09-08 Last updated: 2019-01-18Bibliographically approved
2. Highly branched 2,3-diyne-1-phospha-1,3-butadiene motifs via Pd/Cu mediated alkynyl addition
Open this publication in new window or tab >>Highly branched 2,3-diyne-1-phospha-1,3-butadiene motifs via Pd/Cu mediated alkynyl addition
(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-373905 (URN)
Available from: 2019-01-17 Created: 2019-01-17 Last updated: 2019-01-18
3. Synthesis and Characterization of Cyclopentadithiophene Heterofulvenes: Design Tools for Light-Activated Processes
Open this publication in new window or tab >>Synthesis and Characterization of Cyclopentadithiophene Heterofulvenes: Design Tools for Light-Activated Processes
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2017 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 24, p. 5673-5677Article in journal (Refereed) Published
Abstract [en]

The development of new materials for solar-to-energy conversion should consider stability, ease of fabrication, and beneficial photophysical properties. In this context, a set of novel -conjugated building blocks, with phospha- and arsaalkenes possessing a unique dithienyl annulated heterofulvenoid core, have been prepared as air- and moisture-stable sensitizers. These compounds unify electron-donor and -acceptor moieties, making them potential candidates for light-harvesting applications. Optical characterization of these systems was performed by steady-state and time-resolved absorption spectroscopy, supported by time-dependent DFT calculations. Tuning of the optical properties of these systems can be achieved by varying the pnictogen element at the bridgehead position, giving a bathochromic shift of approximate to 40nm and coordinating the phosphaalkene towards gold Au-I centers. The latter results in a approximate to 2000-fold extension of the approximate to 10ps lifetime of uncoordinated systems well into the ns regime.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2017
Keywords
arsaalkene, electrochemistry, main group elements, phosphaalkene, pnictogens, time-resolved spectroscopy
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-322721 (URN)10.1002/chem.201700917 (DOI)000400044400006 ()28248442 (PubMedID)
Funder
Swedish Research Council, 2013-4763Knut and Alice Wallenberg FoundationÅForsk (Ångpanneföreningen's Foundation for Research and Development)
Available from: 2017-05-29 Created: 2017-05-29 Last updated: 2019-01-18Bibliographically approved

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