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Viologen-based solution-processable ionic porous polymers for electrochromic applications.

Chem Sci

May 2024

Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry and Chemical Engineering, Shaanxi Normal University Xi'an 710119 P. R. China

Electrochromic porous thin films are promising for applications in smart windows and energy-efficient optical displays. However, their generally poor processing ability and excessive processing times remain grand challenges. Herein, we report the design and convenient synthesis of core-altered -arylated viologens with aldehyde groups (πV-CHO) as new building blocks to prepare soluble, viologen-embedded ionic porous polymers.

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Electrochemical Formation of Ionic Porous Organic Polymers Based on Viologen for Electrochromic Applications.

Macromol Rapid Commun

July 2024

International Science & Technology Cooperation Base of Energy Materials and Application, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, P. R. China.

The systematic study of two ionic porous organic polymers (iPOPs) based on viologens and their first applications in the electrochromic field are reported. The viologen-based iPOPs are synthesized by electrochemical polymerization with cyano groups, providing a simple and controllable method for iPOPs that solves the film preparation problems common to viologens. After the characterization of these iPOPs, a detailed study of their electrochromic properties is conducted.

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Trapping Halogen Anions in Cationic Viologen Porous Organic Polymers for Highly Cycling-Stable Cathode Materials.

Small

November 2023

Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.

Halogens, especially Br and I , as cathode materials for lithium-ion batteries exhibit high energy density with low cost, but poor cycling performance due to their high solubility in electrolyte solution. Herein, viologen-based cationic porous organic polymers (TpVXs, X = Cl, Br, or I) with abundant pores and ionic redox-active moieties are designed to immobilize halogen anions stoichiometrically. TpVBr and TpVI electrodes exhibit high initial specific capacity (116 and 132 mAh g at 0.

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A viologen-based porous organic polymer, POP-V-VI, was designed and synthesized by a facile nucleophilic substitution between cyanuric chloride and 1,2-bis(4-pyridinium) ethylene. Together with the reported POP-V-BPY with a similar structure, these viologen-based porous organic polymers bear high charge density, phenyl ring and nitrogenous affinity sites, which endow them with excellent iodine vapor uptake capacity (4860 mg g for POP-V-VI and 4200 mg g for POP-V-BPY) and remarkably high adsorption capacity for pyridine (4470 mg g for POP-V-VI and 8880 mg g for POP-V-BPY) and other aliphatic amines. POP-V-VI and POP-V-BPY could be efficiently recycled and reused three times without significant loss of iodine vapor uptake.

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In this work, we report a series of crystalline viologen-based porous ionic polymers (denoted VIP-X, X = Cl or Br), that have formed dicationic viologens paired with halogen anions and intrinsic hydrogen-bonded water molecules, towards metal-free heterogeneous catalytic conversion of carbon dioxide (CO) under mild conditions. The targeted VIP-X materials were facilely constructed the Menshutkin reaction of 4,4'-bipyridine with 4,4'-bis(bromomethyl)biphenyl (BCBMP) or 4,4'-bis(chloromethyl)biphenyl (BBMBP) monomers. Their crystalline and porous structures, morphological features and chemical structures and compositions were fully characterized by various advanced techniques.

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