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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.2c00419· OSTI ID:1864738
 [1];  [2];  [2];  [3];  [4]
  1. Johns Hopkins Univ., Baltimore, MD (United States); JOhns Hopkins University
  2. Univ. of Oregon, Eugene, OR (United States)
  3. Georgetown Univ., Washington, DC (United States)
  4. Johns Hopkins Univ., Baltimore, MD (United States)
+ Show Author Affiliations
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.
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, Journal Name: Journal of the American Chemical Society Journal Issue: 10 Vol. 144; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Absorption
Delocalization
Molecular modeling
Molecular properties
Polymers