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Tuning the Band Gap of Polyfulvenes by Use of “Handles”: On the Effects of Exocyclic Substitution, Benzannulation, and Ring Methylation.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy.
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(English)Manuscript (preprint) (Other academic)
National Category
Polymer Chemistry Theoretical Chemistry
URN: urn:nbn:se:uu:diva-172872OAI: oai:DiVA.org:uu-172872DiVA: diva2:515947
Available from: 2012-04-16 Created: 2012-04-16 Last updated: 2012-08-01
In thesis
1. Ground and Excited State Aromaticity: Design Tools for π-Conjugated Functional Molecules and Materials
Open this publication in new window or tab >>Ground and Excited State Aromaticity: Design Tools for π-Conjugated Functional Molecules and Materials
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The main focus of this thesis is on the aromaticity of the ground state and electronically excited states of π-conjugated molecules and polymers, as well as how aromaticity is connected to their properties.

The electronic structures of polybenzenoid hydrocarbons (PBHs) were explored through density functional theory (DFT) calculations and the π-component of the electron localization function (ELFπ). The study revealed how the π-electronic structure is influenced by the fusion of double bonds or benzene rings to the PBHs. We also demonstrated that the π-electrons of benzene extend to accommodate as much aromaticity as possible when bond length distorted.  

The aromatic chameleon property displayed by fulvenes, isobenzofulvenes, fulvalenes, bis(fulvene)s, and polyfulvenes were investigated using DFT calculations. The tria-, penta-, and heptafulvenes were shown to possess ionization energies and electron affinities which can be tuned extensively by substitution, some of which even outperform TTF and TCNQ, the prototypical electron donor and acceptor, respectively. The singlet-triplet energy gap of pentafulvenes can be tuned extensively by substitution to the point that the triplet state is lower than the singlet state and thus becomes the ground state. The ELFπ of isobenzofulvene shows that the benzene ring in an electronically excited state can be more aromatic than the corresponding ring in the ground state. We have shown that the 6-ring of [5.6.7]quinarene is influenced by a Hückel aromatic resonance structure with 4n+2 π-electrons in the excited quintet state. The bis(fulvene)s which are composed of a donor type heptafulvene and an acceptor type pentafulvene, retain the basic donor-acceptor properties of the two fragments and could function as compact donor-acceptor dyads. A few of the designed polyfulvenes were found to have band gaps below 1 eV at the PBC-B3LYP/6-31G(d) level.

Various 2,7-disubstituted fluorenones and dibenzofulvenes were synthesized and their excited state properties were investigated by absorption spectroscopy and time-dependent DFT calculations. It was found that the 1A1B transition of ππ* character can be tuned by substitution in the 2,7-positions. The 2,7-bis(N,N-dimethyl) derivatives of fluorenone and dibenzofulvene displayed low energy transitions at 2.18 and 1.61 eV, respectively, in toluene.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2012. 84 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 929
fulvene, fulvalene, polyfulvene, aromaticity, triplet state, excited state, Clar structure, polybenzenoid hydrocarbons (PBH), conjugated polymers, computational chemistry, optical spectroscopy
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
urn:nbn:se:uu:diva-173115 (URN)978-91-554-8362-3 (ISBN)
Public defence
2012-06-05, B42, BMC, Husargatan 3, Uppsala, 09:15 (English)
Available from: 2012-05-14 Created: 2012-04-18 Last updated: 2012-08-01Bibliographically approved

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Dahlstrand, Christian
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