Illuminating mechanochemical reactions by combining real-time fluorescence emission monitoring and periodic time-dependent density-functional calculations

26 October 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

We provide a proof-of-principle demonstration of the first dual-spectroscopic method for direct and real-time observation of mechanochemical reactions by ball milling, supported by high-level molecular and periodic density-functional theory (DFT) calculations, including periodic time-dependent (TD-DFT) calculations to model solid-state fluorescence spectra. By combining standard Raman and fluorescence benchtop spectrometers in a single readily accessible tandem monitoring technique, we simultaneously observe changes to the supramolecular structure during mechanochemical polymorph transformation and cocrystallization of the model pharmaceutical system indometacin. The observed time-resolved in situ spectroscopic data is supported by ex situ X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy measurements. First principles calculations facilitate the interpretation of both real-time spectroscopic and ex situ data by demonstrating how changes in crystalline environment affect vibrational and electronic excited states.

Keywords

Mechanochemistry
Reaction Monitoring
Density Functional Theory
Fluorescence
Ball Milling
Pharmaceuticals
Raman

Supplementary materials

Title
Description
Actions
Title
Supplementary Information for: Illuminating mechanochemical reactions by combining real-time fluorescence emission monitoring and periodic time-dependent density-functional calculations
Description
Supplementary materials characterization including powder diffraction, fluorescence, Raman, solid-state NMR. Fitting of in situ data sets and comparison of DFT simulated and experimental spectra.
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.