Ferroelectricity in a hydrogen-bonded alternating donor–acceptor supramolecular copolymer

Barman, Shubhankar; Bandyopadhyay, Supriya; Ghosh, Anupam; Das, Surajit; Mondal, Tathagata; Datta, Ayan; Ghosh, Suhrit; Datta, Anuja

doi:10.1039/d2cc02506j

Cited by 5 publications

(2 citation statements)

References 36 publications

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“…In order to map the microscopic FE domains of these achiral/chiral mixed systems at a nanoscale, respective films were further probed using piezoresponse force microscopy (PFM) at room temperature. − From the previous discussion, it was expected that increasing the chiral molecule in the mixed sample would clearly show the domain structure at even low bias voltage, particularly due to their short retention time (as discussed in Figure e), and here we present a representative domain switching behavior of the AD 2 A + AD 2 A- C mixed system with the 30:70 composition. Figures and S8 show the representative vertical (out-of-plane) PFM phase, amplitude images, and plots for the 30:70 AD 2 A + AD 2 A- C mixed system.…”

Section: Resultsmentioning

confidence: 95%

Pronounced Chirality Effect on the Ferroelectricity of Hydrogen-Bonded Supramolecular Assemblies of Ambipolar Chromophoric Systems

et al. 2023

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Chirality effects are well documented in different biological functions, but examples in soft materials physics are lesser known. This paper reports a significant chirality effect on modulating ferroelectricity in hydrogen-bonded supramolecular assemblies of two acceptor (A)−donor (D)−acceptor (A)-type conjugated molecules, namely, AD 2 A-C and AD 2 A. Both molecules contain the same naphthalimide−bithiophene− naphthalimide conjugated chromophore, symmetrically functionalized with two substituted benzamide wedges with either a chiral (AD 2 A-C ) or achiral (AD 2 A) peripheral alkyl chain. They exhibit self-assembly in a hydrocarbon solvent methylcyclohexane (MCH), driven by H-bonding among the amide groups and aromatic stacking of the conjugated chromophore. Despite showing similar entangled fibrillar morphology, ultraviolet−visible (UV−vis) and Fourier transform infrared spectroscopy (FT-IR) spectra of the aggregated samples indicate a significant difference in the internal order of the self-assembled AD 2 A-C and AD 2 A. The CD spectra and microscopy images confirm helical assembly for the chiral derivative. In the mixed samples of AD 2 A-C + AD 2 A, chirality induction followed a "sergeant and soldiers" principle. The chiral AD 2 A-C exhibits stable ferroelectricity with a Curie temperature of 361 K and a saturation polarization of ∼2 μC cm −2 , while the achiral AD 2 A lacks any notable ferroelectricity. The retained ferroelectricity in the mixed samples and the polarization tunability through chirality induction support their direct correlation and are key observations for predicting the future soft ferroelectric low-power electronic systems.

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Section: Resultsmentioning

confidence: 95%

Pronounced Chirality Effect on the Ferroelectricity of Hydrogen-Bonded Supramolecular Assemblies of Ambipolar Chromophoric Systems

et al. 2023

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“…Upon UV light irradiation the ferroelectricity was lost as a result of the disassembly of the CT state. Recently we have reported [64] RT ferroelectricity in alternating supramolecular copolymer of amide‐functionalized pyrene (Py‐3) and naphthalene‐diimide (NDI‐2) building blocks (Figure 6). H‐bond stabilized alternating copolymerization between these two molecules produced fibrillar gel in a hydrocarbon solvent such as methyl‐cyclohexane, in which D‐A CT‐interaction was clearly evident from the UV/Vis and other studies.…”

Section: D‐a Charge‐transfer (Ct) Complexesmentioning

confidence: 99%

Supramolecular Organic Ferroelectric Materials from Donor–Acceptor Systems

Barman,

Pal,

Mukherjee

et al. 2023

Chemistry A European J

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Amongst different class of organic systems, donor(D)‐acceptor(A) charge‐transfer (CT)‐ complexes were recognized 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, explored for ferroelectric (FE) phase transitions. Discussion begins with a general introduction of ferroelectricity and different associated parameters. Then it moves on to show early examples of CT‐cocrystals that showed FE properties in sub‐ambient temperature. Subsequently, recent development in the field on 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 and finally it shows very recent development on ferroelectricity in supramolecular assemblies of single‐component dipolar or ambipolar π‐systems, exhibiting intra‐molecular charge transfer. Effect of structural nuances such as H‐bonding, balanced charge‐transfer and chirality on the observed ferroelectricity is described with 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.

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Controlling the Morphological Features, Aspect Ratio and Emission Patterns of Supramolecular Copolymers by Restricted Dimensional Growth

Das

Anand

Vedhanarayanan

et al. 2023

Chemistry A European J

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One of the bottlenecks associated with supramolecular polymerization of functional pi‐systems is the spontaneous assembly of monomers leading to one‐ or two‐dimensional (1D or 2D) polymers without control over chain length and optical properties. In the case of supramolecular copolymerization of monomers that are structurally too diverse, preferential self‐sorting occurs unless they are closely interacting donor‐acceptor pairs. Herein, we establish that the spontaneous 1D polymerization of a phenyleneethynylene (PE) derivative and the 2D polymerization of a Bodipy derivative (BODIPY) can be controlled by copolymerizing them in different ratios, leading to unusual spindle‐shaped structures with controlled aspect ratio, as evident by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and confocal laser scanning microscopy (CLSM) studies. For example, when the content of BODIPY is 50% in the BODIPY‐PE mixture, the 1D polymerization of PE is significantly restricted to form elongated spindle‐like structures having an aspect ratio of 4‐6. The addition of 75% of BODIPY to PE resulted in circular spindles having an aspect ratio of 1‐2.5, thereby completely restricting the 1D polymerization of PE monomers. Moreover, the resultant supramolecular copolymers exhibited morphology and aspect ratio dependent emission features as observed by the time‐resolved emission studies.

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Ferroelectricity in a hydrogen-bonded alternating donor–acceptor supramolecular copolymer

Cited by 5 publications

References 36 publications

Pronounced Chirality Effect on the Ferroelectricity of Hydrogen-Bonded Supramolecular Assemblies of Ambipolar Chromophoric Systems

Pronounced Chirality Effect on the Ferroelectricity of Hydrogen-Bonded Supramolecular Assemblies of Ambipolar Chromophoric Systems

Supramolecular Organic Ferroelectric Materials from Donor–Acceptor Systems

Controlling the Morphological Features, Aspect Ratio and Emission Patterns of Supramolecular Copolymers by Restricted Dimensional Growth

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