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Facile Image Patterning via Sequential Thiol–Michael/Thiol–Yne Click Reactions

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Department of Chemical and Biological Engineering, University of Colorado, UCB 596, Boulder, Colorado 80309, United States
Guangzhou Institute of Advanced Technology, Chinese Academy of Science, Guangzhou 511458, China
§ School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Zhejiang Key Laboratory of Alternative Technologies for Fine Chemicals Process, Shaoxing University, Shaoxing 312000, China
Department of Electrical, Computer and Energy Engineering, University of Colorado, Boulder, Colorado 80309, United States
Cite this: Chem. Mater. 2014, 26, 23, 6819–6826
Publication Date (Web):November 20, 2014
https://doi.org/10.1021/cm5034436
Copyright © 2014 American Chemical Society

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    Abstract

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    Freestanding substrates with high refractive index modulation, good oxygen resistance, and low volume shrinkage are critical in photolithography for the purpose of high density data storage, image patterning and anticounterfeiting. Herein, we demonstrate a novel paradigm of direct holographic image patterning via the radical-mediated thiol–yne click reaction subsequent to the base-catalyzed thiol-Michael addition reaction. With the benefit of a newly synthesized alkyne monomer, 9-(2-((2-(prop-2-yn-1-yloxy)ethyl)thio)ethyl)-9H-carbazole (POETEC), holograms with as high as 96% diffraction efficiency, refractive index modulation of 0.0036, dynamic range of 5.6 per 200 μm and volume shrinkage of 1.1%, are successfully patterned in an aerobic environment. Uniquely and distinctly, an inhibitor is unnecessary to prevent the initiation of the sequential reaction in this framework.

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