Loading…
Understanding the molecular origin of solid-state emitting PMI realized via the detection of hazardous organic peroxides
This work demonstrates the colorimetric and ratiometric fluorogenic detection of harmful organic peroxides (OPs) by using the S–S annulated perylene monoimide (PMISS) mediated emergence of a unique solid-state red-emitting perylene monoimide (PMI) derivative. PMISS dye has been successfully used for...
Saved in:
Published in: | Journal of materials chemistry. C, Materials for optical and electronic devices Materials for optical and electronic devices, 2021-01, Vol.9 (5), p.1778-1785 |
---|---|
Main Authors: | , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
Summary: | This work demonstrates the colorimetric and ratiometric fluorogenic detection of harmful organic peroxides (OPs) by using the S–S annulated perylene monoimide (PMISS) mediated emergence of a unique solid-state red-emitting perylene monoimide (PMI) derivative. PMISS dye has been successfully used for the detection of hazardous and toxic peroxides present in THF and 1,4-dioxane solvents
via
exhibiting a drastic visible color change from blue to red accompanied by a turn-on fluorescence response, thus offering a much-needed method to detect the presence of high-risk OPs. The chemical reaction between PMISS and peroxide present in THF yielded us two new PMISSO and PMISSO
2
derivatives, which were purified, and their structural and optical properties were subsequently investigated using
1
H-NMR, UV-vis absorption, and fluorescence spectroscopy, single-crystal X-ray diffraction analysis (PMISSO
2
only), and calorimetry. Among both species, PMISSO
2
exhibits unique fluorescence behavior in solution and, more notably, in the solid-state, while PMISSO displayed weak fluorescence in solution and inactivity in the solid-state. Single crystal X-ray analysis of PMISSO
2
shows that steric congestion is caused by the molecular motion of one bulky phenoxy-alkyl substituent in the bay position, and this leads to considerable twisting of the PMI π-scaffold supported by C–H⋯O hydrogen bonds between the SO
2
moieties and the 1,6-bay substituents. This type of molecular flexibility, as observed in the bay-substituent, sterically prohibits PMI aggregation in the solid-state, which gives rise to defined vibronic progressions in the solid-state absorption spectra and also enables it to emit bright red fluorescence. Time dependent density functional theory (TD-DFT) calculations obtained for PMISSO
2
of the crystal geometry nicely support the experimental observations made in both bulk and solution states. This outcome has added a novel dimension to studies of fundamental structure–property relationships of relevance in PMI-based organic electronics. |
---|---|
ISSN: | 2050-7526 2050-7534 |
DOI: | 10.1039/D0TC04980H |