Revealing the Origins of Mechanically Induced Fluorescence Changes in Organic Molecular Crystals

Advanced Materials
Liam WilbrahamIlaria Ciofini

Abstract

Mechanofluorochromic molecular materials display a change in fluorescence color through mechanical stress. Complex structure-property relationships in both the crystalline and amorphous phases of these materials govern both the presence and strength of this behavior, which is usually deemed the result of a mechanically induced phase transition. However, the precise nature of the emitting species in each phase is often a matter of speculation, resulting from experimental data that are difficult to interpret, and a lack of an acceptable theoretical model capable of capturing complex environmental effects. With a combined strategy using sophisticated experimental techniques and a new theoretical approach, here the varied mechanofluorochromic behavior of a series of difluoroboron diketonates is shown to be driven by the formation of low-energy exciton traps in the amorphous phase, with a limited number of traps giving rise to the full change in fluorescence color. The results highlight intrinsic structural links between crystalline and amorphous phases, and how these may be exploited for further development of powerful mechanofluorochromic assemblies, in line with modern crystal engineering approaches.

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Citations

Jan 24, 2020·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Yuichi HiraiClémence Allain
May 7, 2020·Chemical Communications : Chem Comm·Jian-Xin WangQing-Zheng Yang
Aug 5, 2020·Nanoscale·Yang XuHuanrong Li
Dec 15, 2018·Chemistry, an Asian Journal·Rachel Crespo-OteroLluís Blancafort
Oct 30, 2020·Physical Chemistry Chemical Physics : PCCP·Amara ChraytehDenis Jacquemin
May 13, 2021·Journal of Computational Chemistry·Davide LuiseIlaria Ciofini
Jun 24, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Laure de ThieulloyAurélie Perrier
Mar 14, 2019·Journal of Chemical Theory and Computation·Miguel RiveraRachel Crespo-Otero
Nov 24, 2020·The Journal of Physical Chemistry. a·Jian-Xin WangQing-Zheng Yang
Aug 6, 2019·The Journal of Physical Chemistry Letters·Marine LouisRémi Métivier
Dec 10, 2019·ACS Omega·Francesco Muniz-MirandaAndrea Pucci
Jan 21, 2022·Physical Chemistry Chemical Physics : PCCP·Alex AzizRachel Crespo-Otero
Sep 16, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Alexandre PoirotSuzanne Fery-Forgues

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