Splitting the Ring: Impact of Ortho and Meta Pi Conjugation Pathways through Disjointed [8]Cycloparaphenylene Electronic Materials

Peterson, Eric; Maust, Ruth L.; Jasti, Ramesh; Kertesz, Miklos; Tovar, John D.

doi:10.1021/jacs.2c00419

Title: Splitting the Ring: Impact of Ortho and Meta Pi Conjugation Pathways through Disjointed [8]Cycloparaphenylene Electronic Materials

Journal Article · Fri Mar 04 00:00:00 EST 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c00419· OSTI ID:1864738

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Johns Hopkins Univ., Baltimore, MD (United States)
Univ. of Oregon, Eugene, OR (United States)
Georgetown Univ., Washington, DC (United States)

In this report, we describe the synthesis and electronic properties of small-molecule and polymeric [8]cycloparaphenylenes ([8]CPPs) with disjointed pi conjugated substituents. Arylene-ethynylene linkers were installed on opposite sides of the [8]CPP nanohoop as separated by three phenyl units on either side such that the monomer systems have syn (C2 symmetry) and anti (C1 symmetry) conformers with a small energy gap (0.1-0.6 kcal/mol). This disjoined substitution pattern necessarily forces delocalization through and around the CPP radial structure. We demonstrate new electronic states from this radial/linear mixing in both the small molecules and the pi extended polymers. Quantum chemical calculations reveal these electronic processes to arise from multiple operative radial/linear conjugation pathways, as the disjoint pattern results in both ortho and meta connections to the CPP ring. Furthermore, these results affirm the unique nature of hybrid radial and linear pi electron delocalization operative in these new conjugation pathways.

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Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019017

OSTI ID:: 1864738

Alternate ID(s):: OSTI ID: 1903196

Journal Information:: Journal of the American Chemical Society, Vol. 144, Issue 10; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Splitting the Ring: Impact of Ortho and Meta Pi Conjugation Pathways through Disjointed [8]Cycloparaphenylene Electronic Materials

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