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Synthesis and Characterization of Cyclopentadithiophene Heterofulvenes: Design Tools for Light-Activated Processes
Lund Univ, Dept Chem Phys, Lund, Sweden..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Lund Univ, Dept Chem Phys, Lund, Sweden..
Lund Univ, Dept Chem Phys, Lund, Sweden..
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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. Vol. 23, no 24, p. 5673-5677
Keywords [en]
arsaalkene, electrochemistry, main group elements, phosphaalkene, pnictogens, time-resolved spectroscopy
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-322721DOI: 10.1002/chem.201700917ISI: 000400044400006PubMedID: 28248442OAI: oai:DiVA.org:uu-322721DiVA, id: diva2:1099130
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
In thesis
1. Low-Coordinate Organopnictogens: Synthesis and Optoelectronic properties
Open this publication in new window or tab >>Low-Coordinate Organopnictogens: Synthesis and Optoelectronic properties
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
Pnictogen, phosphorus, arsenic, phosphaalkenes, arsaalkenes, phospholes, arsoles, alkynes, π-conjugation, PAHs, Fullerene-C60, sumanene, truxene, organic electronics
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-373906 (URN)978-91-513-0558-5 (ISBN)
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

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