Oligothiophenes are π-conjugated semiconducting and fluorescent molecules whose self-assembly properties are widely investigated for application in organic electronics, optoelectronics, biophotonics, and sensing. Here an approach to the preparation of crystalline oligothiophene nano/microfibers is reported based on the use of a “sulfur overrich” quaterthiophene building block, T4S4 , containing in its covalent network all the information needed to promote the directional, π–π stacking-driven, self-assembly of Y-T4S4-Y oligomers into fibers with hierarchical supramolecular arrangement from nano- to microscale. It is shown that when Y varies from unsubstituted thiophene to thiophene substituted with electron-withdrawing groups, a wide redistribution of the molecular electronic charge takes place without substantially affecting the aggregation modalities of the oligomer. In this way, a structurally comparable series of fibers is obtained having progressively varying optical properties, redox potentials, photoconductivity, and type of prevailing charge carriers (from p- to n-type). With the aid of density functional theory (DFT) calculations, combined with powder X-ray diffraction data, a model accounting for the growth of the fibers from molecular to nano- and microscale is proposed.

Controlling the Functional Properties of Oligothiophene Crystalline Nano/Microfibers via Tailoring of the Self-Assembling Molecular Precursors

Di Maria, Francesca;Zangoli, Mattia;Gazzano, Massimo;Gentili, Denis;Zanelli, Alberto;Fermi, Andrea;Bergamini, Giacomo;Mazzaro, Raffaello;Morandi, Vittorio;
2018

Abstract

Oligothiophenes are π-conjugated semiconducting and fluorescent molecules whose self-assembly properties are widely investigated for application in organic electronics, optoelectronics, biophotonics, and sensing. Here an approach to the preparation of crystalline oligothiophene nano/microfibers is reported based on the use of a “sulfur overrich” quaterthiophene building block, T4S4 , containing in its covalent network all the information needed to promote the directional, π–π stacking-driven, self-assembly of Y-T4S4-Y oligomers into fibers with hierarchical supramolecular arrangement from nano- to microscale. It is shown that when Y varies from unsubstituted thiophene to thiophene substituted with electron-withdrawing groups, a wide redistribution of the molecular electronic charge takes place without substantially affecting the aggregation modalities of the oligomer. In this way, a structurally comparable series of fibers is obtained having progressively varying optical properties, redox potentials, photoconductivity, and type of prevailing charge carriers (from p- to n-type). With the aid of density functional theory (DFT) calculations, combined with powder X-ray diffraction data, a model accounting for the growth of the fibers from molecular to nano- and microscale is proposed.
Di Maria, Francesca; Zangoli, Mattia; Gazzano, Massimo; Fabiano, Eduardo; Gentili, Denis; Zanelli, Alberto; Fermi, Andrea; Bergamini, Giacomo; Bonifazi, Davide; Perinot, Andrea; Caironi, Mario; Mazzaro, Raffaello; Morandi, Vittorio; Gigli, Giuseppe; Liscio, Andrea; Barbarella, Giovanna
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11585/668689
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