Abstract

Herein, we have developed an H-bonded network polymer architecture with improved crystallinity and photophysical properties through a supramolecular interaction between carboxylic acid-containing perylenebisimide (PBI) cross-linker and poly(4-vinyl pyridine) (P4VP) polymer chains. The H-bonded supramolecular polymers (SMPs) are thoroughly characterized using 1 H NMR, FTIR, XRD, and AFM studies. The XRD reveals higher molecular packing, long-range ordering, and better crystallinity after supramolecular assembly formation, while AFM confirms the fibril and sphere-like nanostructures in the SMP networks with decreased diameters. The long-range ordering and nanoaggregate structures in SMP benefit the network structure for better diffusion of counter ions during the redox reaction of the PBI moieties. The electrochromic (EC) measurements of the films divulge the similar reversible EC colour change of the PBI and SMP films from pristine red to deep violet along with vis-to-NIR electrochromism between the −2 V to +1 V potential sweeping along with the significant improvement of the EC parameters in SMP films compared to pristine PBI film. The colouring time (red to deep violet) is improved by 63% (5.6 s–2.2 s), while the bleaching time (deep violet to red) is speeded up by 51% (8.4 s–4.1 s) along with the increment in colouration efficiency by 50% (52.3 cm 2 /C to 78.1 cm 2 /C). Therefore, this report is very advantageous to deliver a simple and viable strategy for the enhancement of the EC parameters of organic electrochromes through the generation of ordered H-bonded polymer network formation. • Generation of H-bonded supramolecular polymer assembly (SPA) with perylene bisimide (PBI). • PBI used as cross-linker for H-bonded SPA with poly(4-vinyl pyridine). • SPA shows fast switching and improved colouration efficiency than pristine PBI. • Durable vis-to-NIR electrochromism in PBI based SPA.

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