Molecular Packing Analysis of the Smectic E Phase of a Benzothieno-benzothiophene Derivative by a Combined Experimental / Computational Approach

TL;DR

This study combines experimental X-ray diffraction and computational modeling to analyze the molecular packing in the smectic E phase of a benzothiophene derivative, revealing nano-segregation and preferred herringbone arrangements.

Contribution

It provides detailed molecular packing motifs and insights into nano-segregation in the SmE phase through integrated experimental and computational methods.

Findings

Crystallographic order is greater across layers than along them.

Nano-segregation is present within the SmE phase.

Herringbone packing of aromatic units is energetically favored.

Abstract

The molecule 2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene has gained a lot of attention, since high charge carrier mobility was observed in thin film transistors. Its thermotropic liquid crystalline states may play an important role in the thin film formation, since the smectic A and the smectic E phase (SmE) are claimed to be pre-stages of the final bulk structure. To understand the phase diversity, structural characterisation of solution processed thin films are performed by X-ray diffraction in the complete temperature range up to the isotropic state at 240{\deg}C. The diffraction pattern of the SmE phase is analysed in detail. Peak broadening analysis reveals that the crystallographic order across the smectic layers is larger than the order along the smectic layers. A combined experimental and computational approach is used to determine the molecular packing within the SmE phase. It leads to a number of different packing motifs. A comparison of the calculated diffraction pattern with the experimental results reveals that nano-segregation is present within the SmE phase. Energy consideration clearly favours a herringbone arrangement of the aromatic units. The nano-segregation within the SmE phase with herringbone packing of the aromatic units is accompanied with interdigidation of sidechains from neighbouring smectic layers.