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Non-covalent close contacts in fluorinated thiophene-phenylene-thiophene conjugated units: understanding the nature and dominance of O···H versus S···F and O···F interactions towards the control of polymer conformation

Non-covalent close contacts in fluorinated thiophene-phenylene-thiophene conjugated units: understanding the nature and dominance of O···H versus S···F and O···F interactions towards the control of polymer conformation
Non-covalent close contacts in fluorinated thiophene-phenylene-thiophene conjugated units: understanding the nature and dominance of O···H versus S···F and O···F interactions towards the control of polymer conformation
Using a simple π-conjugated trimer, EDOT-phenylene-EDOT (where EDOT = 3,4-ethylenedioxythiophene), we evaluate the effect that fluorine substituents have upon changes in conformation, conjugation and oxidation potentials in π-conjugated structures. These variations are assessed as a function of the fluorine atom’s propensity to feature in hydrogen and/or halogen bonding with other heteroatoms. The molecular motif was chosen because the EDOT unit presents the possibility of competing O···X or S···X non-covalent contacts (where X = H or F). Such non-bonding interactions are acknowledged to be highly influential in dictating molecular and polymer morphology and inducing changes in certain physical properties. We studied four compounds, beginning with an unsubstituted bridging phenylene ring and then adding one, two, or four fluorine units to the parent molecule. Our studies involve single crystal XRD studies, cyclic voltammetry, absorption spectroscopy and density functional theory calculations to identify the dominant non-covalent interactions and elucidate their effects on the molecules described. Experimental studies have also been carried out on the corresponding electrochemically synthesized polymers to confirm that these non-covalent interactions and their effects persist in polymers. Our findings show that hydrogen bonding and halogen bonding feature in these molecules and their corresponding polymers.
0897-4756
Kharandiuk, Tetiana
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Hussien, Eman J.
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Cameron, Joseph
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Petrina, Romana
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Findlay, Neil J.
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Naumov, Roman
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Klooster, Wim T.
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Coles, Simon J.
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Ai, Qianxiang
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Goodlett, Stephen
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Risko, Chad
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Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd
Kharandiuk, Tetiana
5d366232-b1d9-4fec-9547-9e195533c1c5
Hussien, Eman J.
e2849815-3f32-43b8-8343-42f463396d43
Cameron, Joseph
569f2ded-aded-4c54-a045-556ad9b0cd81
Petrina, Romana
c1acf79a-55a8-477c-b97e-9daa440186a4
Findlay, Neil J.
6f6367a4-3b3c-4fb7-9ee7-3d53ad3dab8a
Naumov, Roman
d11b63f9-f31f-4204-b1cf-3a3c8c2e3bbb
Klooster, Wim T.
64dc0111-f415-4226-9189-45764c0933d9
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Ai, Qianxiang
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Goodlett, Stephen
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Risko, Chad
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Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd

Kharandiuk, Tetiana, Hussien, Eman J., Cameron, Joseph, Petrina, Romana, Findlay, Neil J., Naumov, Roman, Klooster, Wim T., Coles, Simon J., Ai, Qianxiang, Goodlett, Stephen, Risko, Chad and Skabara, Peter J. (2019) Non-covalent close contacts in fluorinated thiophene-phenylene-thiophene conjugated units: understanding the nature and dominance of O···H versus S···F and O···F interactions towards the control of polymer conformation. Chemistry of Materials. (doi:10.1021/acs.chemmater.9b01886).

Record type: Article

Abstract

Using a simple π-conjugated trimer, EDOT-phenylene-EDOT (where EDOT = 3,4-ethylenedioxythiophene), we evaluate the effect that fluorine substituents have upon changes in conformation, conjugation and oxidation potentials in π-conjugated structures. These variations are assessed as a function of the fluorine atom’s propensity to feature in hydrogen and/or halogen bonding with other heteroatoms. The molecular motif was chosen because the EDOT unit presents the possibility of competing O···X or S···X non-covalent contacts (where X = H or F). Such non-bonding interactions are acknowledged to be highly influential in dictating molecular and polymer morphology and inducing changes in certain physical properties. We studied four compounds, beginning with an unsubstituted bridging phenylene ring and then adding one, two, or four fluorine units to the parent molecule. Our studies involve single crystal XRD studies, cyclic voltammetry, absorption spectroscopy and density functional theory calculations to identify the dominant non-covalent interactions and elucidate their effects on the molecules described. Experimental studies have also been carried out on the corresponding electrochemically synthesized polymers to confirm that these non-covalent interactions and their effects persist in polymers. Our findings show that hydrogen bonding and halogen bonding feature in these molecules and their corresponding polymers.

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Accepted/In Press date: 27 June 2019
e-pub ahead of print date: 27 June 2019

Identifiers

Local EPrints ID: 432399
URI: https://eprints.soton.ac.uk/id/eprint/432399
ISSN: 0897-4756
PURE UUID: dedd50ac-7f61-418d-bb46-5bbcf2b1e3dd
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 12 Jul 2019 16:30
Last modified: 20 Jul 2019 01:10

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