Catalyst Halogenation Enables Rapid and Efficient Polymerizations with Visible to Far-Red Light
- 2 August 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 142 (34), 14733-14742
- https://doi.org/10.1021/jacs.0c07136
Abstract
Driving rapid polymerizations with visible to near-infrared light will enable nascent technologies in the emerging fields of bio- and composite-printing. However, current photopolymerization strategies are limited by long reaction times, high light intensities, and/or large catalyst loadings. Improving efficiency remains elusive without a comprehensive, mechanistic evaluation of photocatalysis to better understand how composition relates to polymerization metrics. With this objective in mind, a series of methine- and aza-bridged boron dipyrromethene (BODIPY) derivatives were synthesized and systematically characterized to elucidate key structure-property relationships that facilitate efficient photopolymerization driven by visible to far-red light. For both BODIPY scaffolds, halogenation was shown as a general method to increase polymerization rate, quantitatively characterized using a custom real-time infrared spectroscopy setup. Furthermore, a combination of steady-state emission quenching experiments, electronic structure calculations, and ultrafast transient absorption revealed that efficient intersystem crossing to the lowest excited triplet state upon halogenation was a key mechanistic step to achieving rapid photopolymerization reactions. Unprecedented polymerization rates were achieved with extremely low light intensities (< 1 mW/cm2) and catalyst loadings (< 50 μM), exemplified by reaction completion within 60 seconds of irradiation using green, red, and far-red light-emitting diodes. Halogenated BODIPY photoredox catalysts were additionally employed to produce complex 3D structures using high-resolution visible light 3D printing, demonstrating the broad utility of these catalysts in additive manufacturing.Funding Information
- Welch Foundation (F-1885, F-2007)
- Army Research Office (W911NF1910310)
- Research Corporation for Science Advancement (24489)
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