Single-Molecule Conductance through Hybrid Radially and Linearly π-Conjugated Macromolecules Reveals an Unusual Intramolecular π-Interaction

Shi, Wanzhuo; Wang, Mengjiao; Venkataraman, Latha; Tovar, John D.

doi:10.1021/acs.nanolett.5c03693

Single-Molecule Conductance through Hybrid Radially and Linearly π-Conjugated Macromolecules Reveals an Unusual Intramolecular π-Interaction

Journal Article · Thu Jul 24 00:00:00 EDT 2025 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.5c03693· OSTI ID:2575470

^[1]; Wang, Mengjiao ^[2]; ^[3]; ^[2]

Institute of Science and Technology Austria, Klosterneuberg (Austria)
Johns Hopkins Univ., Baltimore, MD (United States)
Columbia Univ., New York, NY (United States); Institute of Science and Technology Austria, Klosterneuberg (Austria)

We describe the design, synthesis, and single-molecule junction conductance of π-electron molecules bearing both radial and linear π-conjugation pathways, whereby cycloparaphenylene (CPP) radial cores are π-extended linearly with aryl alkyne substituents as models for previously reported CPP-arylene ethynylene conjugated polymers. Although radially and linearly conjugated molecules have been studied previously in isolation as junction-bridging molecular electronic units, this is the first study to examine molecules where both topologies are operative. Our results reveal that the presence of radial CPP components within the junction-spanning pathway leads to a reduction in the conductance of the backbone compared to model linear phenyl substituents. Through tight-binding and DFT-based calculations, we attribute this conductance change to intramolecular van der Waals (vdW) interactions between the CPP ring and the junction-spanning arylene-ethynylene molecular backbone. These interactions induce changes in the dihedral angles of the backbone, leading to a reduced overlap of π orbitals within the molecular junction.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: Basic Energy Sciences; National Science Foundation (NSF)

Grant/Contract Number:: SC0019017

OSTI ID:: 2575470

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 31 Vol. 25; ISSN 1530-6992; ISSN 1530-6984

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Single-Molecule Conductance through Hybrid Radially and Linearly π-Conjugated Macromolecules Reveals an Unusual Intramolecular π-Interaction

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