Issue 10, 2019

Flexible control of excited state transition under pressure/temperature: distinct stimuli-responsive behaviours of two ESIPT polymorphs

Abstract

Realizing fexible and tunable emission conversion in organic solid-state luminescent materials is always fascinating. Herein, we successfully achieved fexible photochemical conversion under pressure and temperature on two types of 4-methyl-2-(5-[4-dimethylaminophenyl]-1H-pyrazole-3-yl)phenol (4MPP) single crystals with distinct aggregation form and geometry showing as green (GC) and blue-violet (BVC). These conversions were studied in detail by fluoresence and Raman spectroscopies, followed with Hirshfeld surface analysis, and this study provides a significant material system for understanding the mechanisms of structural conversion between normal emission (E*) and excited state intramolecular proton transfer (ESIPT, K*) comprehensively under pressure and temperature. Owing to having a proton transferred tautomer, BVC exhibits remarkable changes in its emission feature with pressure increasing to 4.79 GPa, along with the blue-shift and fluorescence enhancement according to a conversion from E* to K*. This compression-induced conversion is proved to be caused by the contraction of the intermolecular distances, the increase of molecular planarization degree, and the enhanced O–H⋯N intramolecular interaction, along with the reduced distance of H⋯N and the elongation of the bond length of O–H. Differently, GC shows rapidly weakened fluorescence and slight blue-shift at a relatively lower pressure (1.01 GPa) based on its more restricted structure. Moreover, GC can realize an excited state transition from K* to E* when lowering its temperature. BVC experiences an abrupt phase transformation to GC at a high temperature of 190 °C. This work discloses the photo-physical properties and stimuli-responsive behaviours of two 4MPP polymorphs, which provides deep insight into the relationship between molecular structure and photoluminescent nature, especially in the crystals with the ESIPT property.

Graphical abstract: Flexible control of excited state transition under pressure/temperature: distinct stimuli-responsive behaviours of two ESIPT polymorphs

Supplementary files

Article information

Article type
Research Article
Submitted
18 iyn 2019
Accepted
19 avq 2019
First published
22 avq 2019

Mater. Chem. Front., 2019,3, 2128-2136

Flexible control of excited state transition under pressure/temperature: distinct stimuli-responsive behaviours of two ESIPT polymorphs

A. Li, H. Liu, C. Song, Y. Geng, S. Xu, H. Zhang, H. Zhang, H. Cui and W. Xu, Mater. Chem. Front., 2019, 3, 2128 DOI: 10.1039/C9QM00395A

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