Illuminating milling mechanochemistry by tandem real-time fluorescence emission and Raman spectroscopy monitoring

Patrick A. Julien; Mihails Arhangelskis; Luzia S. Germann; Martin Etter; Robert E. Dinnebier; Andrew J. Morris; Tomislav Friščić

doi:10.1039/d3sc04082h

Illuminating milling mechanochemistry by tandem real-time fluorescence emission and Raman spectroscopy monitoring

Patrick A. Julien^*, Mihails Arhangelskis^*, Luzia S. Germann, Martin Etter, Robert E. Dinnebier, Andrew J. Morris^*, Tomislav Friščić^*

^*Corresponding author for this work

Metallurgy and Materials

Research output: Contribution to journal › Article › peer-review

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Abstract

In pursuit of accessible and interpretable methods for direct and real-time observation of mechanochemical reactions, we demonstrate a tandem spectroscopic method for monitoring of ball-milling transformations combining fluorescence emission and Raman spectroscopy, accompanied by high-level molecular and periodic density-functional theory (DFT) calculations, including periodic time-dependent (TD-DFT) modelling of solid-state fluorescence spectra. This proof-of-principle report presents this readily accessible dual-spectroscopy technique as capable of observing changes to the supramolecular structure of the model pharmaceutical system indometacin during mechanochemical polymorph transformation and cocrystallisation. The observed time-resolved in situ spectroscopic and kinetic data are supported by ex situ X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy measurements. The application of first principles (ab initio) calculations enabled the elucidation of how changes in crystalline environment, that result from mechanochemical reactions, affect vibrational and electronic excited states of molecules. The herein explored interpretation of both real-time and ex situ spectroscopic data through ab initio calculations provides an entry into developing a detailed mechanistic understanding of mechanochemical milling processes and highlights the challenges of using real-time spectroscopy.

Original language	English
Pages (from-to)	12121-12132
Journal	Chemical Science
Volume	14
DOIs	https://doi.org/10.1039/d3sc04082h
Publication status	Published - 12 Oct 2023

Bibliographical note

We thank the support of NSERC Discovery Grant RGPIN-2017-06467, Discovery Accelerator Grant (SMFSU 507837-17), Tier-1 Canada Research Chair Program, the University of Birmingham, and Leverhulme International Professorship (TF). MA thanks the support of NCN (Poland), Opus Grant 2020/37/B/ST5/02638. LSG acknowledges financial support from the Swiss National Science Foundation (Grant P2SKP2_187638). We thank WestGrid and Compute Canada for providing access to Cedar supercomputer. We are grateful for computational support from the UK National High Performance Computing Service, ARCHER, for which access was obtained via the UKCP consortium and funded by EPSRC grant ref EP/K013564/1. We thank McGill Chemistry Characterisation Facility for instrument use. We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, beamline P02.1. The authors acknowledge networking support via the EPSRC Collaborative Computational Projects, CCP9 (EP/M022595/1) and CCP-NC (EP/T026642/1).

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10.1039/d3sc04082hLicence: Creative Commons: Attribution (CC BY)

JulienP2023IlluminatingFinal published version, 2.62 MBLicence: Creative Commons: Attribution (CC BY)

Collaborative Computational Project in NMR Crystallography
Morris, A.
Engineering & Physical Science Research Council
6/05/20 → 5/05/25
Project: Research Councils

Cite this

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title = "Illuminating milling mechanochemistry by tandem real-time fluorescence emission and Raman spectroscopy monitoring",

abstract = "In pursuit of accessible and interpretable methods for direct and real-time observation of mechanochemical reactions, we demonstrate a tandem spectroscopic method for monitoring of ball-milling transformations combining fluorescence emission and Raman spectroscopy, accompanied by high-level molecular and periodic density-functional theory (DFT) calculations, including periodic time-dependent (TD-DFT) modelling of solid-state fluorescence spectra. This proof-of-principle report presents this readily accessible dual-spectroscopy technique as capable of observing changes to the supramolecular structure of the model pharmaceutical system indometacin during mechanochemical polymorph transformation and cocrystallisation. The observed time-resolved in situ spectroscopic and kinetic data are supported by ex situ X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy measurements. The application of first principles (ab initio) calculations enabled the elucidation of how changes in crystalline environment, that result from mechanochemical reactions, affect vibrational and electronic excited states of molecules. The herein explored interpretation of both real-time and ex situ spectroscopic data through ab initio calculations provides an entry into developing a detailed mechanistic understanding of mechanochemical milling processes and highlights the challenges of using real-time spectroscopy.",

author = "Julien, {Patrick A.} and Mihails Arhangelskis and Germann, {Luzia S.} and Martin Etter and Dinnebier, {Robert E.} and Morris, {Andrew J.} and Tomislav Fri{\v s}{\v c}i{\'c}",

note = "We thank the support of NSERC Discovery Grant RGPIN-2017-06467, Discovery Accelerator Grant (SMFSU 507837-17), Tier-1 Canada Research Chair Program, the University of Birmingham, and Leverhulme International Professorship (TF). MA thanks the support of NCN (Poland), Opus Grant 2020/37/B/ST5/02638. LSG acknowledges financial support from the Swiss National Science Foundation (Grant P2SKP2_187638). We thank WestGrid and Compute Canada for providing access to Cedar supercomputer. We are grateful for computational support from the UK National High Performance Computing Service, ARCHER, for which access was obtained via the UKCP consortium and funded by EPSRC grant ref EP/K013564/1. We thank McGill Chemistry Characterisation Facility for instrument use. We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, beamline P02.1. The authors acknowledge networking support via the EPSRC Collaborative Computational Projects, CCP9 (EP/M022595/1) and CCP-NC (EP/T026642/1).",

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month = oct,

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doi = "10.1039/d3sc04082h",

language = "English",

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publisher = "Royal Society of Chemistry",

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T1 - Illuminating milling mechanochemistry by tandem real-time fluorescence emission and Raman spectroscopy monitoring

AU - Julien, Patrick A.

AU - Arhangelskis, Mihails

AU - Germann, Luzia S.

AU - Etter, Martin

AU - Dinnebier, Robert E.

AU - Morris, Andrew J.

AU - Friščić, Tomislav

N1 - We thank the support of NSERC Discovery Grant RGPIN-2017-06467, Discovery Accelerator Grant (SMFSU 507837-17), Tier-1 Canada Research Chair Program, the University of Birmingham, and Leverhulme International Professorship (TF). MA thanks the support of NCN (Poland), Opus Grant 2020/37/B/ST5/02638. LSG acknowledges financial support from the Swiss National Science Foundation (Grant P2SKP2_187638). We thank WestGrid and Compute Canada for providing access to Cedar supercomputer. We are grateful for computational support from the UK National High Performance Computing Service, ARCHER, for which access was obtained via the UKCP consortium and funded by EPSRC grant ref EP/K013564/1. We thank McGill Chemistry Characterisation Facility for instrument use. We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, beamline P02.1. The authors acknowledge networking support via the EPSRC Collaborative Computational Projects, CCP9 (EP/M022595/1) and CCP-NC (EP/T026642/1).

PY - 2023/10/12

Y1 - 2023/10/12

N2 - In pursuit of accessible and interpretable methods for direct and real-time observation of mechanochemical reactions, we demonstrate a tandem spectroscopic method for monitoring of ball-milling transformations combining fluorescence emission and Raman spectroscopy, accompanied by high-level molecular and periodic density-functional theory (DFT) calculations, including periodic time-dependent (TD-DFT) modelling of solid-state fluorescence spectra. This proof-of-principle report presents this readily accessible dual-spectroscopy technique as capable of observing changes to the supramolecular structure of the model pharmaceutical system indometacin during mechanochemical polymorph transformation and cocrystallisation. The observed time-resolved in situ spectroscopic and kinetic data are supported by ex situ X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy measurements. The application of first principles (ab initio) calculations enabled the elucidation of how changes in crystalline environment, that result from mechanochemical reactions, affect vibrational and electronic excited states of molecules. The herein explored interpretation of both real-time and ex situ spectroscopic data through ab initio calculations provides an entry into developing a detailed mechanistic understanding of mechanochemical milling processes and highlights the challenges of using real-time spectroscopy.

AB - In pursuit of accessible and interpretable methods for direct and real-time observation of mechanochemical reactions, we demonstrate a tandem spectroscopic method for monitoring of ball-milling transformations combining fluorescence emission and Raman spectroscopy, accompanied by high-level molecular and periodic density-functional theory (DFT) calculations, including periodic time-dependent (TD-DFT) modelling of solid-state fluorescence spectra. This proof-of-principle report presents this readily accessible dual-spectroscopy technique as capable of observing changes to the supramolecular structure of the model pharmaceutical system indometacin during mechanochemical polymorph transformation and cocrystallisation. The observed time-resolved in situ spectroscopic and kinetic data are supported by ex situ X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy measurements. The application of first principles (ab initio) calculations enabled the elucidation of how changes in crystalline environment, that result from mechanochemical reactions, affect vibrational and electronic excited states of molecules. The herein explored interpretation of both real-time and ex situ spectroscopic data through ab initio calculations provides an entry into developing a detailed mechanistic understanding of mechanochemical milling processes and highlights the challenges of using real-time spectroscopy.

U2 - 10.1039/d3sc04082h

DO - 10.1039/d3sc04082h

M3 - Article

SN - 2041-6520

VL - 14

SP - 12121

EP - 12132

JO - Chemical Science

JF - Chemical Science

ER -

Illuminating milling mechanochemistry by tandem real-time fluorescence emission and Raman spectroscopy monitoring

Abstract

Bibliographical note

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Collaborative Computational Project in NMR Crystallography

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