Guest-Mediated Hierarchical Self-Assembly of Dissymmetric Organic Cages to Form Supramolecular Ferroelectrics

Abstract

We herein report on the guest-responsive hierarchical self-assembly of dissymmetric cage DC-1 with intrinsic dipole along its C 3 -symmetric axis. DC-1 molecules self-assemble into supramolecular columns with the molecular dipoles aligned along the columnar axis. Mediated by different host-guest interactions of ethyl acetate (EtOAc) and chloroform (CHCl 3 ), the columns are arranged in an anti-parallel and parallel fashion, respectively, leading to a switch of centrosymmetric and non-centrosymmetric superstructures. The symmetry of the molecular packing of DC-1 molecules of the non-centrosymmetric crystalline phase is therefore broken, producing a supramolecular ferroelectric with second-harmonic generation and piezoelectric responses. We demonstrate that cages could serve as promising building blocks for the discovery of supramolecular materials with emergent functions and properties, including but not limited to, organic ferroelectrics and non-linear optics.

Supramolecular Proton Conductors Self-Assembled by Organic Cages

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Recent advances in the applications of porous organic cages

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“…(b) Vertical PFM amplitude (butterfly) and phase (hysteresis) loops as a function of dc bias. Domain switching of this thin film presented with (c) PFM amplitude image and (d) phase image within a 10 Â 10 mm region, recorded after applying a voltage of +50 V on the left side and À50 V on the right side of the region 135.…”

Crystalline microporous small molecule semiconductors based on porphyrin for high-performance chemiresistive gas sensing

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