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

Bulgarevich, Kirill; Takimiya, Kazuo

doi:10.1039/d3mh01055d

Cited by 1 publication

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“…In other words, choosing molecules that crystallize into the brickwork structure seems not to be a final solution to realize 2D electronic structures. Thus, for further advancement of crystal structure control, the simulation of a crystal structure sufficiently accurate for the estimation of solid-state electronic structure will be a critical issue in the future. ,− …”

Section: Methylthiolation On Peri-condensed Pahsmentioning

confidence: 99%

Crystal-Structure Control of Molecular Semiconductors by Methylthiolation: Toward Ultrahigh Mobility

Takimiya,

Bulgarevich,

Kawabata

2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS: The crystal structure of organic semiconductors has been regarded as one of the crucial factors for realizing highperformance electronic devices, such as organic field-effect transistors. However, although the control of crystal structures of organic semiconductors has been examined in the last two decades of intensive efforts of the development of organic semiconductors, active measures to control crystal structures enabling high carrier mobility are still limited. In 2016, our research group noticed that regioselective methylthiolation could provide a selective crystal structure change from an ordinary herringbone structure to a pitched π-stacking structure, similar to the crystal structure of rubrene, in the benzo[1,2-b:4,5-b′]dithiophene (BDT) system. Following this serendipitous finding, our group systematically investigated the relationship between the molecular and crystal structures of a range of methylthiolated aromatic and heteroaromatic compounds. This Account provides a comprehensive overview of our research efforts and advancements in the development of methylthiolated small-molecule-based organic semiconductors (molecular semiconductors). We first describe the outline of the past development of molecular semiconductors, focusing on the types of crystal structures of high-performance molecular semiconductors. Then, we describe our findings on the drastic crystal structure change in the BDT system upon methylthiolation, detailing the causes of the change in terms of the intermolecular contacts and intermolecular interaction energies. This is followed by the confirmation of the generality of the crystal-structure change by methylthiolation of a series of acene and heteroacenes, where the herringbone structure in the parent system is unexceptionally transformed into the pitched π-stacking structure, a promising crystal structure for highmobility molecular semiconductors well exemplified by the prototypical molecular semiconductor, rubrene. In fact, the methylthiolated anthradithiophene afforded comparable high mobility to rubrene in single-crystal field-effect transistors. Then, we demonstrate that the sandwich herringbone structures of peri-condensed polycyclic aromatic hydrocarbons, including pyrene, perylene, and peropyrene, change into brickwork crystal structures upon methylthiolation and that, among these compounds, very promising molecular semiconductors, methylthiolated pyrene and peropyrene, showing ultrahigh mobility of 30 cm 2 V s −1 , are realized.Through the studies, by gaining insights into the underlying mechanisms driving the crystal structure changes, we lay a strong foundation for tackling challenges related to controlling the crystal structures and developing high-performance molecular semiconductors. This will be a distinct approach from the past activities in the development of molecular semiconductors that mainly focused on molecules themselves, including their synthesis, properties, and characterization....

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Section: Methylthiolation On Peri-condensed Pahsmentioning

confidence: 99%

Crystal-Structure Control of Molecular Semiconductors by Methylthiolation: Toward Ultrahigh Mobility

Takimiya,

Bulgarevich,

Kawabata

2024

Acc. Chem. Res.

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

Abstract: We demonstrate the simulation of brickwork-related polymorphs with conditional branching for methylthiolated peri-condensed polycyclic aromatic hydrocarbons, which allows us to discuss the likelihood of the appearance of each polymorph.

Cited by 1 publication

References 39 publications

Crystal-Structure Control of Molecular Semiconductors by Methylthiolation: Toward Ultrahigh Mobility

Crystal-Structure Control of Molecular Semiconductors by Methylthiolation: Toward Ultrahigh Mobility

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