Issue 31, 2024

Preparation of intrinsically fragile bent crystals

Abstract

Although molecular crystals have long been considered to be intrinsically brittle, a study of molecular crystals that are capable of plastic or elastic bending upon applying mechanical stress recently attracted significant attention. Malleable molecular crystals often need to meet specific criteria regarding the intermolecular interaction patterns within the crystal structure. Accordingly, examples have been reported where one polymorph shows bending, while other polymorphs of the same compound exhibit fracturing upon exposure to mechanical force. Here, we have succeeded in preparing bent crystals of an intrinsically fragile polymorph. Methylated flufenamic acid (1) can form three different polymorphs, i.e., , , and , of which is difficult to isolate. Under mechanical force, the crystals of exhibit remarkable plastic deformation, while those of are readily broken. Similar to the mechanical properties, the emission properties of 1 differ depending on the polymorph, i.e., exhibits a shorter-wavelength emission maximum and much higher emission quantum yield than . Remarkably, both the unbent and bent forms of the crystals can undergo a phase transition to the phase upon exposure to ethyl acetate. In this manner, phase transitions of the mechanically bent crystals of polymorph afforded bent crystals of the intrinsically fragile polymorph . These findings may lead to a potential post-modification method for the preparation of functional flexible materials with enhanced emission properties in order to expand their applications.

Graphical abstract: Preparation of intrinsically fragile bent crystals

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Article information

Article type
Edge Article
Submitted
03 maj 2024
Accepted
06 jul 2024
First published
11 jul 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 12258-12263

Preparation of intrinsically fragile bent crystals

T. Seki, S. Kobayashi, R. Ishikawa, K. Yano, T. Matsuo and S. Hayashi, Chem. Sci., 2024, 15, 12258 DOI: 10.1039/D4SC02918F

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