Cold photo-carving of halogen-bonded co-crystals of a dye and a volatile co-former using visible light

T. H. Borchers; F. Topić; J. C. Christopherson; O. S. Bushuyev; J. Vainauskas; H. M. Titi; T. Friščić; C. J. Barrett

doi:10.1038/s41557-022-00909-0

Cold photo-carving of halogen-bonded co-crystals of a dye and a volatile co-former using visible light

T. H. Borchers, F. Topić, J. C. Christopherson, O. S. Bushuyev, J. Vainauskas, H. M. Titi, T. Friščić^*, C. J. Barrett^*

^*Corresponding author for this work

Chemistry

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

7 Citations (Scopus)

Abstract

The formation of co-crystals by the assembly of molecules with complementary molecular recognition functionalities is a popular strategy to design or improve a range of solid-state properties, including those relevant for pharmaceuticals, photo- or thermoresponsive materials and organic electronics. Here, we report halogen-bonded co-crystals of a fluorinated azobenzene derivative with a volatile component—either dioxane or pyrazine—that can be cut, carved or engraved with low-power visible light. This cold photo-carving process is enabled by the co-crystallization of a light-absorbing azo dye with a volatile component, which gives rise to materials that can be selectively disassembled with micrometre precision using low-power, non-burning laser irradiation or a commercial confocal microscope. The ability to shape co-crystals in three dimensions using laser powers of 0.5–20 mW—substantially lower than those used for metals, ceramics or polymers—is rationalized by photo-carving that targets the disruption of weak supramolecular interactions, rather than the covalent bonds or ionic structures targeted by conventional laser beam or focused ion beam machining processes. [Figure not available: see fulltext.]

Original language	English
Pages (from-to)	574-581
Number of pages	8
Journal	Nature Chemistry
Volume	14
Issue number	5
Early online date	31 Mar 2022
DOIs	https://doi.org/10.1038/s41557-022-00909-0
Publication status	Published - May 2022

Bibliographical note

Funding Information:
We thank the Natural Sciences and Engineering Research Council (NSERC) Canada for their financial support of this work through Discovery Grants RGPIN-2019-05661 (C.J.B.), RGPIN-2017-06467 (T.F.) and Discovery Accelerator award RGPAS 507837-17 (T.F.), as well as the Government of Canada for a Tier-1 Canada Research Chair (T.F.), and Vanier Graduate (O.S.B.) and Banting Postdoctoral (F.T.) Fellowships. The funders had no role in the study design, data collection and analysis, decision to publish or preparation of the manuscript. We thank M. J. Harrington of McGill Chemistry for use of the confocal Raman microscope, R. D. Rogers of the University of Alabama for the use of a high-speed camera and S. Borchers for the image of the laser source used in Fig. . We acknowledge the use of the Cedar supercomputer, enabled by WestGrid and Compute Canada.

Publisher Copyright:
© 2022, The Author(s), under exclusive licence to Springer Nature Limited.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering

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10.1038/s41557-022-00909-0

Cite this

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title = "Cold photo-carving of halogen-bonded co-crystals of a dye and a volatile co-former using visible light",

abstract = "The formation of co-crystals by the assembly of molecules with complementary molecular recognition functionalities is a popular strategy to design or improve a range of solid-state properties, including those relevant for pharmaceuticals, photo- or thermoresponsive materials and organic electronics. Here, we report halogen-bonded co-crystals of a fluorinated azobenzene derivative with a volatile component—either dioxane or pyrazine—that can be cut, carved or engraved with low-power visible light. This cold photo-carving process is enabled by the co-crystallization of a light-absorbing azo dye with a volatile component, which gives rise to materials that can be selectively disassembled with micrometre precision using low-power, non-burning laser irradiation or a commercial confocal microscope. The ability to shape co-crystals in three dimensions using laser powers of 0.5–20 mW—substantially lower than those used for metals, ceramics or polymers—is rationalized by photo-carving that targets the disruption of weak supramolecular interactions, rather than the covalent bonds or ionic structures targeted by conventional laser beam or focused ion beam machining processes. [Figure not available: see fulltext.]",

author = "Borchers, {T. H.} and F. Topi{\'c} and Christopherson, {J. C.} and Bushuyev, {O. S.} and J. Vainauskas and Titi, {H. M.} and T. Fri{\v s}{\v c}i{\'c} and Barrett, {C. J.}",

note = "Funding Information: We thank the Natural Sciences and Engineering Research Council (NSERC) Canada for their financial support of this work through Discovery Grants RGPIN-2019-05661 (C.J.B.), RGPIN-2017-06467 (T.F.) and Discovery Accelerator award RGPAS 507837-17 (T.F.), as well as the Government of Canada for a Tier-1 Canada Research Chair (T.F.), and Vanier Graduate (O.S.B.) and Banting Postdoctoral (F.T.) Fellowships. The funders had no role in the study design, data collection and analysis, decision to publish or preparation of the manuscript. We thank M. J. Harrington of McGill Chemistry for use of the confocal Raman microscope, R. D. Rogers of the University of Alabama for the use of a high-speed camera and S. Borchers for the image of the laser source used in Fig. . We acknowledge the use of the Cedar supercomputer, enabled by WestGrid and Compute Canada. Publisher Copyright: {\textcopyright} 2022, The Author(s), under exclusive licence to Springer Nature Limited.",

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AU - Bushuyev, O. S.

AU - Vainauskas, J.

AU - Titi, H. M.

AU - Friščić, T.

AU - Barrett, C. J.

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N2 - The formation of co-crystals by the assembly of molecules with complementary molecular recognition functionalities is a popular strategy to design or improve a range of solid-state properties, including those relevant for pharmaceuticals, photo- or thermoresponsive materials and organic electronics. Here, we report halogen-bonded co-crystals of a fluorinated azobenzene derivative with a volatile component—either dioxane or pyrazine—that can be cut, carved or engraved with low-power visible light. This cold photo-carving process is enabled by the co-crystallization of a light-absorbing azo dye with a volatile component, which gives rise to materials that can be selectively disassembled with micrometre precision using low-power, non-burning laser irradiation or a commercial confocal microscope. The ability to shape co-crystals in three dimensions using laser powers of 0.5–20 mW—substantially lower than those used for metals, ceramics or polymers—is rationalized by photo-carving that targets the disruption of weak supramolecular interactions, rather than the covalent bonds or ionic structures targeted by conventional laser beam or focused ion beam machining processes. [Figure not available: see fulltext.]

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Cold photo-carving of halogen-bonded co-crystals of a dye and a volatile co-former using visible light

Abstract

Bibliographical note

ASJC Scopus subject areas

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