A Molecular Strategy to Lock-in the Conformation of a Perylene Bisimide-Derived Supramolecular Polymer.

electrochemistry excitonic properties perylene bisimide semiconducting nanomaterials supramolecular polymer

Journal

Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543

Informations de publication

Date de publication:
04 May 2020
Historique:
received: 14 09 2019
revised: 21 12 2019
pubmed: 28 1 2020
medline: 28 1 2020
entrez: 28 1 2020
Statut: ppublish

Résumé

Locking-in the conformation of supramolecular assemblies provides a new avenue to regulate the (opto)electronic properties of robust nanoscale objects. In the present contribution, we show that the covalent tethering of a perylene bisimide (PBI)-derived supramolecular polymer with a molecular locker enables the formation of a locked superstructure equipped with emergent structure-function relationships. Experiments that exploit variable-temperature ground-state electronic absorption spectroscopy unambiguously demonstrate that the excitonic coupling between nearest neighboring units in the tethered superstructure is preserved at a temperature (371 K) where the pristine, non-covalent assembly exists exclusively in a molecularly dissolved state. A close examination of the solid-state morphologies reveals that the locked superstructure engenders the formation of hierarchical 1D materials which are not achievable by unlocked assemblies. To complement these structural attributes, we further demonstrate that covalently tethering a supramolecular polymer built from PBI subunits enables the emergence of electronic properties not evidenced in non-covalent assemblies. Using cyclic voltammetry experiments, the elucidation of the potentiometric properties of the locked superstructure reveals a 100-mV stabilization of the conduction band energy when compared to that recorded for the non-covalent assembly.

Identifiants

pubmed: 31984605
doi: 10.1002/anie.201911780
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

7487-7493

Subventions

Organisme : The Arnold and Mabel Beckman Foundation
ID : BYI2018

Informations de copyright

© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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Auteurs

Adam Ashcraft (A)

Department of Chemistry, The University of Miami, 1301 Memorial Drive, Cox Science Building, Coral Gables, FL, 33146, USA.

Kaixuan Liu (K)

Department of Chemistry, The University of Miami, 1301 Memorial Drive, Cox Science Building, Coral Gables, FL, 33146, USA.

Arindam Mukhopadhyay (A)

Department of Chemistry, The University of Miami, 1301 Memorial Drive, Cox Science Building, Coral Gables, FL, 33146, USA.

Victor Paulino (V)

Department of Chemistry, The University of Miami, 1301 Memorial Drive, Cox Science Building, Coral Gables, FL, 33146, USA.

Chuan Liu (C)

Department of Chemistry, The University of Miami, 1301 Memorial Drive, Cox Science Building, Coral Gables, FL, 33146, USA.

Brianna Bernard (B)

Department of Chemistry, The University of Miami, 1301 Memorial Drive, Cox Science Building, Coral Gables, FL, 33146, USA.

Dalia Husainy (D)

Department of Chemistry, The University of Miami, 1301 Memorial Drive, Cox Science Building, Coral Gables, FL, 33146, USA.

Tina Phan (T)

Department of Chemistry, The University of Miami, 1301 Memorial Drive, Cox Science Building, Coral Gables, FL, 33146, USA.

Jean-Hubert Olivier (JH)

Department of Chemistry, The University of Miami, 1301 Memorial Drive, Cox Science Building, Coral Gables, FL, 33146, USA.

Classifications MeSH