Hydrogen-Bond-Promoted Planar Conformation, Crystallinity, and Charge Transport in Semiconducting Diazaisoindigo Derivatives

Mu, Anthony U.; Kim, Yeon-Ju; Miranda, Octavio; Vazquez, Mariela; Strzalka, Joseph; Xu, Jie; Fang, Lei

doi:10.1021/acsmaterialslett.2c00179

Title: Hydrogen-Bond-Promoted Planar Conformation, Crystallinity, and Charge Transport in Semiconducting Diazaisoindigo Derivatives

Journal Article · Mon May 30 20:00:00 EDT 2022 · ACS Materials Letters

DOI: https://doi.org/10.1021/acsmaterialslett.2c00179 · OSTI ID:1905885

Mu, Anthony U. ^[1]; Kim, Yeon-Ju ^[2]; Miranda, Octavio ^[1]; Vazquez, Mariela ^[1];

^[2];

^[1]

Texas A & M Univ., College Station, TX (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

Conformational control of π-conjugated molecules using intramolecular noncovalent bonds represents a promising strategy to tailor the solid-state molecular packing and electronic properties of these materials. Here, we report the design and synthesis of two model compounds featuring intramolecular hydrogen bonds formed between a center diazaisoindigo unit (the acceptor) and flanking indole units (the donor). Computational and experimental investigations show that these hydrogen bonds enthalpically stabilize the coplanar molecular conformation by over 10 kcal/mol. The formation of these hydrogen bonds is also slightly favorable in terms of entropy, ensuring high temperature stability of the planar conformation. In this work, thermal annealing of thin films of these compounds imparts high crystallinity and orientation in the solid state, while the non-hydrogen bond control only gave an amorphous solid. Field-effect transistor devices fabricated from these thin films exhibit hole mobilities up to 0.270 cm² V^-1 s^-1, in contrast to the lack of measurable charge carrier mobility for the non-hydrogen bond control. This work demonstrates an efficient synthetic strategy to incorporate robust intramolecular hydrogen bonds into conjugated π-systems and elucidates the mechanism on how such hydrogen bonds promote the desired molecular conformation, solid-state packing, and electronic performances of conjugated organic materials.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1905885

Journal Information:: ACS Materials Letters, Journal Name: ACS Materials Letters Journal Issue: 7 Vol. 4; ISSN 2639-4979

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

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Charge transport
Conformation
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Thin films

Title: Hydrogen-Bond-Promoted Planar Conformation, Crystallinity, and Charge Transport in Semiconducting Diazaisoindigo Derivatives

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