Supramolecular Organic Ferroelectric Materials from Donor–Acceptor Systems

Abstract Organic ferroelectric (FE) materials, though known for more than a century, are yet to reach close to the benchmark of inorganic or hybrid materials in terms of the magnitude of polarization. Amongst the different classes of organic systems, donor (D)–acceptor (A) charge‐transfer (CT) complexes are recognized as promising for ferroelectricity owing to their neutral‐to‐ionic phase transition at low temperature. This review presents an overview of different supramolecular D‐A systems that have been explored for FE phase transitions. The discussion begins with a general introduction of ferroelectricity and its different associated parameters. Then it moves on to show early examples of CT cocrystals that have shown FE properties at sub‐ambient temperature. Subsequently, recent developments in the field of room temperature (RT) ferroelectricity, exhibited by H‐bond‐stabilized lock‐arm supramolecular‐ordering (LASO) in D‐A co‐crystals or other FE CT‐crystals devoid of neutral‐ionic phase transition are discussed. Then the discussion moves on to emerging reports on other D‐A soft materials such as gel and foldable polymers; finally it shows very recent developments in ferroelectricity in supramolecular assemblies of single‐component dipolar or ambipolar π‐systems, exhibiting intra‐molecular charge transfer. The effects of structural nuances such as H‐bonding, balanced charge transfer and chirality on the observed ferroelectricity is described with the available examples. Finally, piezoelectricity in recently reported ambipolar ADA‐type systems are discussed to highlight the future potential of these soft materials in micropower energy harvesting.