Visible-Light-Driven "On"/"Off" Photochromism of a Polyoxometalate Diarylethene Coordination Complex

Journal of the American Chemical Society
Jingjing XuChris Ritchie

Abstract

Herein we report the first photochromic polyoxometalate (POM)-based diarylethene (DAE) coordination complex, prepared by ligation of two cobalt(III)-incorporated borotungstates [BIIIWVI11O39CoIII]6- with the ditopic pyridyl-containing diarylethene (C25H16N2F6S2). The solution-state composition, structure, and stability of the assembly were probed using 1H and 19F nuclear magnetic resonance spectroscopy (NMR), electrospray ionization quadrupolar time-of-flight mass spectrometry (ESI-QTOF-MS), ultraviolet-visible spectroscopy (UV-vis), and small-angle X-ray scattering (SAXS), revealing that the complex self-organizes to adopt a molecular dumbbell structure due to electrostatic and steric considerations. This conformation is a prerequisite for the photocyclization reaction. The assembly was found to be switchable between two states using visible light due to the perturbation of the DAE electronic structure on coordination to the POM. We present photophysical data, including the reaction quantum efficiency of the molecular switch in both directions measured using a custom-built quantum yield determination setup in addition to fatigue resistance on prolonged irradiation.

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Citations

Aug 9, 2019·Chemistry : a European Journal·Amandine BoulmierOlivier Oms
Jun 20, 2020·Chemical Communications : Chem Comm·Elizabeth HampsonGraham N Newton
Jun 11, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Dinesh G PatelFrank A Novak
Jun 10, 2021·Small·Aminuddin Bin Ahmad KayaniMadhu Bhaskaran
Mar 27, 2019·ACS Applied Materials & Interfaces·Yongqi YangGuanghui Gao
Jan 4, 2020·The Journal of Organic Chemistry·Dinesh G PatelFrank A Novak
Dec 7, 2021·ACS Applied Materials & Interfaces·Ying WuYu Liu
Dec 30, 2021·Chemistry : a European Journal·Hao WangQuan Li

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