Oxacycle-Fused [1]Benzothieno[3,2-b][1]benzothiophene Derivatives: Synthesis, Electronic Structure, Electrochemical Properties, Ionisation Potential, and Crystal Structure

Meera Mohankumar; Basab Chattopadhyay; Rachid Hadji; Lionel Sanguinet; Alan R. Kennedy; Vincent Lemaur; Jérôme Cornil; Oliver Fenwick; Paolo Samorì; Yves Geerts

doi:10.1002/cplu.201800346

Oxacycle-Fused [1]Benzothieno[3,2-b][1]benzothiophene Derivatives: Synthesis, Electronic Structure, Electrochemical Properties, Ionisation Potential, and Crystal Structure

Meera Mohankumar, Basab Chattopadhyay, Rachid Hadji, Lionel Sanguinet, Alan R. Kennedy, Vincent Lemaur, Jérôme Cornil, Oliver Fenwick, Paolo Samorì, Yves Geerts

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

The molecular properties of [1]benzothieno[3,2-b][1]benzothiophene (BTBT) are vulnerable to structural modifications, which in turn are determined by the functionalization of the backbone. Hence versatile synthetic strategies are needed to discover the properties of this molecule. To address this, we have attempted heteroatom (oxygen) functionalization of BTBT by a concise and easily scalable synthesis. Fourfold hydroxy-substituted BTBT is the key intermediate, from which the compounds 2,3,7,8-bis(ethylenedioxy)-[1]benzothieno[3,2-b][1]benzothiophene and 2,3,7,8-bis(methylenedioxy)-[1]benzothieno[3,2-b][1]benzothiophene are synthesized. The difference in ether functionalities on the BTBT scaffold influences the ionisation potential values substantially. The crystal structure reveals the transformation of the herringbone motif in bare BTBT towards π-stacked columns in the newly synthesized derivatives. The results are further justified by the simulated HOMO levels of the model compound.

Original language	English
Pages (from-to)	1263-1269
Number of pages	7
Journal	ChemPlusChem
Volume	84
Issue number	9
DOIs	https://doi.org/10.1002/cplu.201800346
State	Published - 1 Sep 2019
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Funding

The authors acknowledge support from the Belgian National Fund for Scientific Research (FNRS – PDR T.0058.14). B. C. kindly acknowledges support from the FRS-FNRS (Belgian National Scientific Research Fund) for the POLYGRAD Project 22333186. B. C. is a FRS-FNRS Research Fellow. P.S. acknowledges also the Agence Nationale de la Recherche through the LabEx CSC (ANR-10-LABX-0026_CSC) and the International Center for Frontier Research in Chemistry (icFRC). The work in the Laboratory for Chemistry of Novel Materials was supported by the European Commission/Région Wallonne (FEDER – BIORGEL project), the Interuniversity Attraction Pole program of the Belgian Federal Science Policy Office (PAI 7/05), the Programme d'Excellence de la Région Wallonne (OPTI2MAT project), the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (FRS.-FNRS) under Grant No. 2.5020.11, and FRS-FNRS. J. C. is a FNRS Research Director.

Funders	Funder number
ANR-10-LABX-0026_CSC
Consortium des Équipements de Calcul Intensif
European Commission/Région Wallonne
Centre International de Recherche aux Frontières de la Chimie
Agence Nationale de la Recherche
Fonds De La Recherche Scientifique - FNRS	2.5020.11, PDR T.0058.14, 22333186
Belgian Federal Science Policy Office	PAI 7/05
European Regional Development Fund
LabEx Chimie des Systèmes Complexes

Keywords

arenes
crystal engineering
electrochemistry
electronic properties
π-conjugation

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10.1002/cplu.201800346

Cite this

Mohankumar, M., Chattopadhyay, B., Hadji, R., Sanguinet, L., Kennedy, A. R., Lemaur, V., Cornil, J., Fenwick, O., Samorì, P., & Geerts, Y. (2019). Oxacycle-Fused [1]Benzothieno[3,2-b][1]benzothiophene Derivatives: Synthesis, Electronic Structure, Electrochemical Properties, Ionisation Potential, and Crystal Structure. ChemPlusChem, 84(9), 1263-1269. https://doi.org/10.1002/cplu.201800346

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abstract = "The molecular properties of [1]benzothieno[3,2-b][1]benzothiophene (BTBT) are vulnerable to structural modifications, which in turn are determined by the functionalization of the backbone. Hence versatile synthetic strategies are needed to discover the properties of this molecule. To address this, we have attempted heteroatom (oxygen) functionalization of BTBT by a concise and easily scalable synthesis. Fourfold hydroxy-substituted BTBT is the key intermediate, from which the compounds 2,3,7,8-bis(ethylenedioxy)-[1]benzothieno[3,2-b][1]benzothiophene and 2,3,7,8-bis(methylenedioxy)-[1]benzothieno[3,2-b][1]benzothiophene are synthesized. The difference in ether functionalities on the BTBT scaffold influences the ionisation potential values substantially. The crystal structure reveals the transformation of the herringbone motif in bare BTBT towards π-stacked columns in the newly synthesized derivatives. The results are further justified by the simulated HOMO levels of the model compound.",

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Mohankumar, M, Chattopadhyay, B, Hadji, R, Sanguinet, L, Kennedy, AR, Lemaur, V, Cornil, J, Fenwick, O, Samorì, P & Geerts, Y 2019, 'Oxacycle-Fused [1]Benzothieno[3,2-b][1]benzothiophene Derivatives: Synthesis, Electronic Structure, Electrochemical Properties, Ionisation Potential, and Crystal Structure', ChemPlusChem, vol. 84, no. 9, pp. 1263-1269. https://doi.org/10.1002/cplu.201800346

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AU - Chattopadhyay, Basab

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Oxacycle-Fused [1]Benzothieno[3,2-b][1]benzothiophene Derivatives: Synthesis, Electronic Structure, Electrochemical Properties, Ionisation Potential, and Crystal Structure

Abstract

Bibliographical note

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Keywords

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