TY - JOUR

T1 - Synthesis of covalently linked oligo(phenyleneethynylene) wires incorporating dithiafulvene units

T2 - redox-active "H-cruciforms"

AU - Jørgensen, Frederik Præstholm

AU - Petersen, Johannes Fabritius

AU - Andersen, Cecilie Lindholm

AU - Skov, Anders Bo

AU - Jevric, Martyn

AU - Hammerich, Ole

AU - Nielsen, Mogens Brøndsted

PY - 2017

Y1 - 2017

N2 - Controlled alignment and self-assembly of molecular wires is one of the challenges in the field of molecular electronics. Here, we take an approach by which two oligo(phenyleneethynylene)s (OPEs) are linked together through one vinylogous linker. These molecules thus incorporate a central stilbene part from which the two OPE wires propagate in a so-called "H-cruciform"-like motif. Each ring of the central stilbene unit also contains a redox-active dithiafulvene (DTF) unit and this part of the molecule can thus be considered as an extended tetrathiafulvalene (TTF). Here, we present how such H-cruciforms based on OPE3 and OPE5 molecular wires are prepared by Sonogashira coupling reactions and how the OPEs are functionalized with thioester end-caps as potential electrode anchoring groups. The optical and redox properties of these molecules are also presented. Unsymmetrical systems are achieved by subjecting a differentially protected diethynyl-substituted derivative of terephthalaldehyde to a phosphite-mediated coupling reaction in the presence of a 1,3-dithiol-2-thione. This reaction forms the central stilbene-extended TTF with alkyne substituents and relies on an "umpolung" of the para substituents from electron-withdrawing CHO groups to electron-donating DTF groups in a conversion also promoted by the phosphite.

AB - Controlled alignment and self-assembly of molecular wires is one of the challenges in the field of molecular electronics. Here, we take an approach by which two oligo(phenyleneethynylene)s (OPEs) are linked together through one vinylogous linker. These molecules thus incorporate a central stilbene part from which the two OPE wires propagate in a so-called "H-cruciform"-like motif. Each ring of the central stilbene unit also contains a redox-active dithiafulvene (DTF) unit and this part of the molecule can thus be considered as an extended tetrathiafulvalene (TTF). Here, we present how such H-cruciforms based on OPE3 and OPE5 molecular wires are prepared by Sonogashira coupling reactions and how the OPEs are functionalized with thioester end-caps as potential electrode anchoring groups. The optical and redox properties of these molecules are also presented. Unsymmetrical systems are achieved by subjecting a differentially protected diethynyl-substituted derivative of terephthalaldehyde to a phosphite-mediated coupling reaction in the presence of a 1,3-dithiol-2-thione. This reaction forms the central stilbene-extended TTF with alkyne substituents and relies on an "umpolung" of the para substituents from electron-withdrawing CHO groups to electron-donating DTF groups in a conversion also promoted by the phosphite.

KW - Acylation

KW - Alkynes

KW - Cross-coupling

KW - Molecular electronics

KW - Redox chemistry

U2 - 10.1002/ejoc.201601367

DO - 10.1002/ejoc.201601367

M3 - Journal article

AN - SCOPUS:85006728535

VL - 2017

SP - 1253

EP - 1261

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

SN - 1434-193X

IS - 9

ER -