Nanoribbons or weakly connected acenes? The influence of pyrene insertion on linearly extended ring systems

Ai, Qianxiang; Smith, Tanner; Liyanage, A. Thilanga; Mazza, Samuel M.; Parkin, Sean R.; Anthony, John E.; Risko, Chad

doi:10.1039/d1tc05193h

Title: Nanoribbons or weakly connected acenes? The influence of pyrene insertion on linearly extended ring systems

Journal Article · Thu Nov 18 00:00:00 UTC 2021 · Journal of Materials Chemistry C

DOI: https://doi.org/10.1039/d1tc05193h · OSTI ID:1982230

^[1]; Smith, Tanner ^[1]; Liyanage, A. Thilanga ^[1]; Mazza, Samuel M. ^[1];

^[1];

^[1]

University of Kentucky, Lexington, KY (United States)

Derived from the lateral fusion of benzene rings, acenes are a class of π-conjugated molecules containing a single aromatic sextet, where system size is inversely correlated with chemical stability. In the pursuit of creating graphene nanoribbons/nanowires, several extended-ring structures have been synthesized through linear combinations of azaacenes and pyrene. Importantly, these extended systems demonstrate enhanced chemical stability and allow for the construction of macromolecular-sized structures. In this report we present a combined quantum-chemical and experimental study to reveal the cost of these improved characteristics in fully carbon-based systems. The results clearly show that pyrene moieties inserted among acene units do not result in long acene-like structures, rather the pyrene-inserted acene is, electronically, a series of (nearly) isolated acenes. The origin of pyrene's electronic blocking effect and implications on oxidized and photoexcited states of these extended-ring systems are detailed. The results of this investigation definitively show that coupling pyrene in an orthogonal orientation (through the 4, 5/9, 10 positions or e/l faces) to acenes should be eschewed if nanographene-/nanowire-like structures are desired.

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Research Organization:: University of Kentucky, Lexington, KY (United States)

Sponsoring Organization:: Office of Naval Research (ONR); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI ID:: 1982230

Journal Information:: Journal of Materials Chemistry C, Journal Name: Journal of Materials Chemistry C Journal Issue: 47 Vol. 9; ISSN 2050-7526

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Nanoribbons or weakly connected acenes? The influence of pyrene insertion on linearly extended ring systems

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