Single-molecule conductance through hybrid radially and linearly π-conjugated macromolecules reveals an unusual intramolecular π-interaction Shi, Wanzhuo Wang, Mengjiao Venkataraman, Latha ; https://orcid.org/0000-0002-6957-6089 Tovar, John D. ddc:540 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. American Chemical Society 2025 info:eu-repo/semantics/article doc-type:article text http://purl.org/coar/resource_type/c_2df8fbb1 https://research-explorer.ista.ac.at/record/20221 https://research-explorer.ista.ac.at/download/20221/20269 Shi W, Wang M, Venkataraman L, Tovar JD. Single-molecule conductance through hybrid radially and linearly π-conjugated macromolecules reveals an unusual intramolecular π-interaction. <i>Nano Letters</i>. 2025;25(31):12101-12106. doi:<a href="https://doi.org/10.1021/acs.nanolett.5c03693">10.1021/acs.nanolett.5c03693</a> eng info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.nanolett.5c03693 info:eu-repo/semantics/altIdentifier/e-issn/1530-6992 info:eu-repo/semantics/altIdentifier/wos/001537145800001 info:eu-repo/semantics/altIdentifier/pmid/40707400 info:eu-repo/semantics/openAccess