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Architecting layered molecular packing in substituted benzobisbenzothiophene (BBBT) semiconductor crystals

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Abstract

The construction and control of 2D layered packing motifs with π-extended fused-ring molecules is of crucial importance for developing organic electronic materials and devices. Herein, we demonstrate that, when adequately substituted, two kinds of layered packing motifs are obtainable for benzo[1,2-b:4,5-b′]bis[b]benzothiophene (BBBT), which itself does not show layered crystallinity. We synthesized BBBT derivatives substituted with a combination of alkyl chains and a phenyl ring in a symmetric/asymmetric manner, 2,8-didecyl-BBBT (diC10-BBBT) and 2-decyl-8-phenyl-BBBT (Ph-BBBT-C10). We found that diC10-BBBT forms a layered π-stack (LπS) structure mainly composed of slipped parallel stacks, while Ph-BBBT-C10 forms a typical layered herringbone (LHB) packing structure chiefly composed of T-shaped contacts. This feature is associated with the non-layered packing motif in BBBT: typical π-stack and herringbone structures, both of whose polymorphs show a large slip along the molecular long axis. Calculations of intermolecular interaction energies between neighbouring molecules in the crystals reveal that the interchain interactions suppress the long-axis slip, leading to the formation of the LπS and the LHB, respectively. Both diC10-BBBT and Ph-BBBT-C10 form uniform (ultra)thin films originating from the layered crystallinity, and exhibit good transistor characteristics with a hole mobility of about 1 cm2 V−1 s−1. We discuss how the substituent modifications are useful as crystal engineering to explore the potential of π-extended molecules for electronic applications.

Graphical abstract: Architecting layered molecular packing in substituted benzobisbenzothiophene (BBBT) semiconductor crystals

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Supplementary files

Article information


Submitted
26 Feb 2020
Accepted
19 Apr 2020
First published
20 Apr 2020

CrystEngComm, 2020, Advance Article
Article type
Paper

Architecting layered molecular packing in substituted benzobisbenzothiophene (BBBT) semiconductor crystals

T. Higashino, S. Arai, S. Inoue, S. Tsuzuki, Y. Shimoi, S. Horiuchi, T. Hasegawa and R. Azumi, CrystEngComm, 2020, Advance Article , DOI: 10.1039/D0CE00285B

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