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Mechanically Gated Formation of Donor–Acceptor Stenhouse Adducts Enabling Mechanochemical Multicolor Soft Lithography

Overholts, Anna C. and Granados Razo, Wendy and Robb, Maxwell J. (2022) Mechanically Gated Formation of Donor–Acceptor Stenhouse Adducts Enabling Mechanochemical Multicolor Soft Lithography. ChemRxiv . (Submitted) https://resolver.caltech.edu/CaltechAUTHORS:20220406-223020037

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Abstract

Mechanochromism is one of the most widely developed areas in the quickly emerging field of polymer mechanochemistry. Stress-sensitive molecules called mechanophores are designed to undergo productive chemical transformations in response to mechanical force including changes in color that are useful for sensing and patterning. A variety of mechanochromic mechanophores have been developed, but modulating the photophysical properties of the mechanically generated dyes generally requires the independent preparation of discrete derivatives. Here we introduce a mechanophore platform enabling mechanically gated multicolor chromogenic reactivity. The mechanophore is based on an activated furan precursor to donor–acceptor Stenhouse adducts (DASAs) masked as a hetero-Diels–Alder adduct. Mechanochemical activation of the mechanophore unveils the DASA precursor and subsequent reaction with a secondary amine generates an intensely colored DASA photoswitch. Critically, the color and photochemical properties of the DASA are controlled by the identity of the amine and thus a single mechanophore can be differentiated post-activation to produce a wide range of functionally diverse DASA compounds. We highlight the unique reactivity of this system by establishing the concept of mechanochemical multicolor soft lithography whereby a complex multicolor composite image is printed into a mechanochemically active elastomer through an iterative process of localized compression and reaction with different amines. Our results demonstrate the first example of multicolor pattern reproduction from a single mechanophore, empowering the fabrication of complex stimuli-responsive materials and paving the way for applications in patterning, sensing, and encryption.


Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription
https://doi.org/10.26434/chemrxiv-2022-f09r0DOIDiscussion Paper
ORCID:
AuthorORCID
Overholts, Anna C.0000-0002-0593-6903
Robb, Maxwell J.0000-0002-0528-9857
Additional Information:The content is available under CC BY NC ND 4.0 License. Financial support from Caltech is gratefully acknowledged. A.C.O. was supported by a NSF Graduate Research Fellowship (DGE-1745301) and an Institute Fellowship. We thank Dr. Mona Shahgholi for technical assistance with mass spectrometry and Michael Takase for assistance with X-ray crystallography. Data Availability. All data are available in the manuscript or the Supplementary Information. Experimental data and characterization data for all new compounds prepared in the course of these studies are provided in the Supplementary Information of this manuscript. The X-ray crystallographic coordinates for compound (±)-3 have been deposited at the Cambridge Crystallographic Data Center (CCDC) with deposition #2163133. These data can be obtained free of charge from the Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/structures/. Author Contributions. M.J.R. conceptualized the project and provided guidance during all stages. A.C.O. and M.J.R. designed the research. A.C.O. and W.G.R. performed the experiments. A.C.O., W.G.R., and M.J.R. analyzed the data. A.C.O and M.J.R wrote the manuscript. The authors declare no competing financial interests.
Funders:
Funding AgencyGrant Number
CaltechUNSPECIFIED
NSF Graduate Research FellowshipDGE-1745301
Subject Keywords:polymer mechanochemistry; mechanophore; DASA photoswitch; soft lithography
DOI:10.26434/chemrxiv-2022-f09r0
Record Number:CaltechAUTHORS:20220406-223020037
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220406-223020037
Official Citation:Overholts AC, Granados Razo W, Robb MJ. Mechanically Gated Formation of Donor–Acceptor Stenhouse Adducts Enabling Mechanochemical Multicolor Soft Lithography. ChemRxiv. 2022. doi:10.26434/chemrxiv-2022-f09r0
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114182
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:06 Apr 2022 13:36
Last Modified:24 Oct 2022 23:20

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  • Overholts, Anna C. and Granados Razo, Wendy and Robb, Maxwell J. Mechanically Gated Formation of Donor–Acceptor Stenhouse Adducts Enabling Mechanochemical Multicolor Soft Lithography. (deposited 06 Apr 2022 13:36) [Currently Displayed]

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