Dataset Information

Synthesis and folding behaviour of poly(p-phenylene vinylene)-based ?-sheet polychromophores.

ABSTRACT: This contribution describes the design and synthesis of ?-sheet-mimicking synthetic polymers comprising distinct poly(p-phenylene vinylene) (PPV) and poly(norbornene) (PNB) backbones with multiple turns. The rod-coil-coil-rod tetrablock copolymers, synthesized using ring-opening metathesis polymerization (ROMP) and featuring orthogonal face-to-face ?-? stacking and phenyl/perfluorophenyl interactions, show persistent folding both in bulk and at the single molecule level, irrespective of the number of ?-turns. Single molecule polarization studies reveal that the copolymers are more anisotropic than the corresponding homopolymers. Examination of the spectral signatures of the single molecules shows a dominant emissive chromophore in the linked materials compared to the homopolymer. The lack of significant spectral changes of the folded materials along with the existence of a dominant emission spectrum supports the proposed structure of well-aligned, minimally-interacting chromophores. Utilization of this reliably folding, phenyl/perfluorophenyl functionality could provide an extremely useful tool in future functional materials design.

SUBMITTER: Elacqua E

PROVIDER: S-EPMC6385485 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

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Synthesis and folding behaviour of poly(<i>p</i>-phenylene vinylene)-based β-sheet polychromophores.

Elacqua Elizabeth E Geberth Geoffrey T GT Vanden Bout David A DA Weck Marcus M

Chemical science 20181220 7

This contribution describes the design and synthesis of β-sheet-mimicking synthetic polymers comprising distinct poly(<i>p</i>-phenylene vinylene) (PPV) and poly(norbornene) (PNB) backbones with multiple turns. The rod-coil-coil-rod tetrablock copolymers, synthesized using ring-opening metathesis polymerization (ROMP) and featuring orthogonal face-to-face π-π stacking and phenyl/perfluorophenyl interactions, show persistent folding both in bulk and at the single molecule level, irrespective of t ...[more]

PMID: 30881638

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Project description:The self-assembly of foldamers into macrocycles is a simple approach to non-biological higher-order structure. Previous work on the co-assembly of ortho-phenylene foldamers with rod-shaped linkers has shown that folding and self-assembly affect each other; that is, the combination leads to new emergent behavior, such as access to otherwise unfavorable folding states. To this point this relationship has been passive. Here, we demonstrate control of self-assembly by manipulating the foldamers' conformational energy surfaces. A series of o-phenylene decamers and octamers have been assembled into macrocycles using imine condensation. Product distributions were analyzed by gel-permeation chromatography and molecular geometries extracted from a combination of NMR spectroscopy and computational chemistry. The assembly of o-phenylene decamers functionalized with alkoxy groups or hydrogens gives both [2 + 2] and [3 + 3] macrocycles. The mixture results from a subtle balance of entropic and enthalpic effects in these systems: the smaller [2 + 2] macrocycles are entropically favored but require the oligomer to misfold, whereas a perfectly folded decamer fits well within the larger [3 + 3] macrocycle that is entropically disfavored. Changing the substituents to fluoro groups, however, shifts assembly quantitatively to the [3 + 3] macrocycle products, even though the structural changes are well-removed from the functional groups directly participating in bond formation. The electron-withdrawing groups favor folding in these systems by strengthening arene-arene stacking interactions, increasing the enthalpic penalty to misfolding. The architectural changes are substantial even though the chemical perturbation is small: analogous o-phenylene octamers do not fit within macrocycles when perfectly folded, and quantitatively misfold to give small macrocycles regardless of substitution. Taken together, these results represent both a high level of structural control in structurally complex foldamer systems and the demonstration of large-amplitude structural changes as a consequence of a small structural effects.

Dataset Information

Synthesis and folding behaviour of poly(p-phenylene vinylene)-based ?-sheet polychromophores.

Publications

Synthesis and folding behaviour of poly(<i>p</i>-phenylene vinylene)-based β-sheet polychromophores.

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