Altering Polarization Attributes in Ferroelectric Metallo-Cavitands by Varying Hydrated Alkali-Metal Guest Cations

Srivastava, AKK, Vijayakanth, T, Divya, P, Praveenkumar, B, Steiner, A ORCID: 0000-0002-4315-6123 and Ramamoorthy, B (2017) Altering Polarization Attributes in Ferroelectric Metallo-Cavitands by Varying Hydrated Alkali-Metal Guest Cations J. Mater. Chem. C, 5 (29). pp. 10624-10629. ISSN 2050-7526, 2050-7534

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Abstract

Supramolecular ferroelectrics have emerged as an exciting topic of research for both fundamental understanding and practical applications in the areas of energy and electronics. Here, we describe the synthesis of two metallo-cavitands [{M<inf>4</inf>L<inf>8</inf>(H<inf>2</inf>O)<inf>8</inf>}⊃9(H<inf>2</inf>O)]·(NO<inf>3</inf>)<inf>8</inf>·x(H<inf>2</inf>O) [MNi²⁺ (1) or Co²⁺ (2)] and demonstrate solid-state host-guest behavior and ferroelectricity in the presence of various hydrated alkali metal cations (Hy-A) in their intrinsic voids. Due to the confinement effects of the cavitands, the degree of hydration observed for these alkali metal ions is on the upper side; in particular, the K⁺, Rb⁺ and Cs⁺ ions show high hydration numbers of 8, 9 and 10, respectively. Ferroelectric studies on 1, [Hy-A]⊂1 and [Hy-A]⊂2 assemblies show remnant polarization (P<inf>r</inf>) values ranging from 27 to 30 μC cm^-2 with concomitant variations in the coercive field (E<inf>c</inf>) values at a lower frequency of 0.1 Hz. The observed features for the P-E loop characteristics of all the assemblies are reminiscent of triglycine sulphate (TGS) and certain other supramolecular ferroelectrics. Interestingly, ferroelectric fatigue measurements on all these systems show sizable variations as the cavitands with hard Li⁺ ions exhibiting the maximum (fatigue) tolerance and the ones with higher polarizable Cs⁺ ions show a reduction in P<inf>r</inf> values up to 35%, after 10⁵ switching cycles. The results signify the effect of encapsulated guest molecules in altering the polarization attributes (P<inf>r</inf>, E<inf>c</inf> and fatigue tolerance) via host-guest interactions.

Item Type:	Article
Additional Information:	crosscheck: This document is CrossCheck deposited related_data: Supplementary Information copyright_licence: The Royal Society of Chemistry has an exclusive publication licence for this journal history: Received 21 April 2017; Accepted 4 July 2017; Accepted Manuscript published 5 July 2017
Uncontrolled Keywords:	3402 Inorganic Chemistry, 3403 Macromolecular and Materials Chemistry, 34 Chemical Sciences, 7 Affordable and Clean Energy
Depositing User:	Symplectic Admin
Date Deposited:	10 Aug 2017 14:32
Last Modified:	01 Mar 2026 08:43
DOI:	10.1039/C7TC01758H
Related Websites:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3008901
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