A Molecular Strategy to Lock‐in the Conformation of a Perylene Bisimide‐Derived Supramolecular Polymer. (11th March 2020)

• Record Type: Journal Article
• Authors: Ashcraft, Adam; Liu, Kaixuan; Mukhopadhyay, Arindam; Paulino, Victor; Liu, Chuan; Bernard, Brianna; Husainy, Dalia; Phan, Tina; Olivier, Jean‐Hubert
• Is Part Of: Angewandte Chemie. Volume 132:Number 19(2020)
• Page Start: 7557
• Page End: 7563
• Publication Date: 2020-03-11
• Subjects: Elektrochemie -- Excitonische Eigenschaften -- Perylenbisimid -- Halbleiter-Nanomaterialien -- Supramolekulare Polymere; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201911780
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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. Abstract : Arretieren der Konformation supramolekularer Polymere liefert eine neue Klasse von robusten, π‐konjugierten nanoskaligen Objekten. Spektroskopische und elektrochemische Messungen geben Einblick in die einzigartigen optoelektronischen Eigenschaften dieser Halbleiter‐Überstrukturen.