Oxacycle fused [1]benzothieno[3,2‐b][1]benzothiophene derivatives : synthesis, electronic structure, electrochemical properties, ionisation potential, and crystal structure

Mohankumar, Meera and Chattopadhyay, Basab and Sanguinet, Lionel and Kennedy, Alan R. and Lemaur, Vincent and Cornil, Jérôme and Fenwick, Oliver and Samori, Paolo and Geerts, Yves and Hadji, Rachid (2018) Oxacycle fused [1]benzothieno[3,2‐b][1]benzothiophene derivatives : synthesis, electronic structure, electrochemical properties, ionisation potential, and crystal structure. ChemPlusChem. ISSN 2192-6506

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    Abstract

    he molecular properties of [1]benzothieno[3,2‐b][1]benzothiophene (BTBT) are vulnerable to the structural modifications which in turn are decided 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. Four‐fold 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 elaborated with the aid of quantum chemical calculations.