Crystal‐Structure Simulation of Methylthiolated Peri‐Condensed Polycyclic Aromatic Hydrocarbons for Identifying Promising Molecular Semiconductors: Discovery of 1,3,8,10‐tetrakis(methylthio)peropyrene Showing Ultrahigh Mobility

Abstract

The crystal structures of molecular semiconductors critically affect their carrier transport properties. One of the promising crystal structures that afford high carrier mobility is a brickwork structure recently reported for 1,3,6,8‐tetrakis(methylthio)pyrene (MT‐pyrene) showing ultrahigh mobility. However, such ultrahigh mobility was not realized in other methylchalocogenated pyrenes, owing to subtle differences in the molecular positions in their crystal structures. This means that, for developing superior molecular semiconductors, it is desirable to simulate the crystal structure with sufficient quality before time‐consuming and labor‐intensive synthetic trials.To realize this, we developed a new computational approach to simulating crystal structures of all methylchalocogenated pyrenes, which was then applied to MT‐pyrene‐related methylthiolated peri‐condensed polycyclic aromatic hydrocarbons including perylene, peropyrene, and terrylene derivatives. Among these, 1,3,8,10‐tetrakis(methylthio)peropyrene (MT‐peropyrene) was expected to show high mobility based on the simulated crystal structures. We thus chose MT‐peropyrene as the synthetic target and developed a new peropyrene synthesis method. Thus synthesized MT‐peropyrene has virtually the same crystal structure as the simulated one, and its single‐crystal field‐effect transistors showed mobility as high as 30 cm2 V–1 s–1 and band‐like transport behaviors. These results indicate that the present crystal‐structure simulation is a powerful tool for exploring promising molecular semiconductors.This article is protected by copyright. All rights reserved

Crystal-structure simulation of molecular semiconductors: brickwork-related crystal structures of methylthiolated peri-condensed polycyclic aromatic hydrocarbons

“…2a bottom). 34 On the other hand, in the iBW structure with the monoclinic P 2 1 / n space group, the relationship between the neighboring BW layers is the glide operation. Note that all the molecules in each BW layer in the iBW structure are related by the translation operation similar to that of the BW structure.…”

“…5), there generally exist two ways to pile the BW layers up, as already reported in the previous paper. 34 Fig. 7 shows the case of MT-pyrene as an example.…”

“…1) turned out to be another ultra-high mobility molecular semiconductor (m B 30 cm 2 V À1 s À1 ). 34 From these results, it is safe to say that methylchalcogenolated peri-condensed PAHs generally afford the BW crystal structure. In fact, recently synthesized methylthiolated perylene (MT-perylene, Fig.…”

“…Inspired by these results, we have developed a simple protocol for the simulation of BW crystal structures of unknown methylchalcogenolated peri -condensed PAHs. 34 This protocol, which we call “ in silico crystallization (ISC)” helped us to select a synthetic target, and in fact, thus selected and then synthesized MT-peropyrene (Fig. 1) turned out to be another ultra-high mobility molecular semiconductor ( μ ∼ 30 cm 2 V −1 s −1 ).…”

“…1) turned out to be another ultra-high mobility molecular semiconductor ( μ ∼ 30 cm 2 V −1 s −1 ). 34…”