Superoxide radical generator based on triphenylamine-based supramolecular organic framework for green light photocatalysis.

A novel triphenylamine-based SOF was constructed, which can serve as superoxide radical generator to promote the oxidative hydroxylation of arylboronic acids under green light in water. [Display omitted] • A novel triphenylamine-based SOF was constructed based on the host–guest interaction. • The control of singlet oxygen and superoxide radical can be realized by using SOF as photosensitizers. • The monomer TP-3Py can effectively produce singlet oxygen (1O 2) and realize the photocatalytic oxidation of thioanisole in water. • The TP-SOF has the ability to generate superoxide anion radicals (O 2 •−) efficiently. • TP-SOF can be used for the promotion of the oxidative hydroxylation of arylboronic acids under green light in water. Supramolecular organic frameworks (SOFs) mostly require high-energy purple or blue light for photocatalytic reactions, while highly abundant and low-energy light systems have rarely been explored. Therefore, it is necessary to construct 2D SOFs for low-energy light-induced photocatalysis. This study describes the design and synthesis of a water-soluble two-dimensional (2D) supramolecular organic framework (TP-SOF) using the host–guest interaction between a triphenylamine derivative (TP-3Py) and cucurbit[8]uril (CB[8]). The formation of the 2D SOF can be attributed to the synergistic impact resulting from the orientated head-to-tail superposition mode between the vinylpyridine arms of TP-3Py and CB[8], which results in a significant redshift in the UV–vis absorption spectrum, especially displaying a strong absorption band in the green light region. The monomeric TP-3Py can effectively produce singlet oxygen (1O 2) and realize the photocatalytic oxidation of thioanisole in the aqueous solution. In comparison to monomeric TP-3Py, the confinement effect of CB[8] results in a notable enhancement in the production efficiency of superoxide anion radicals (O 2 •−), exhibiting promising prospects in the field of photocatalytic oxidation reaction, which facilitates the application of TP-SOF as a very efficient photosensitizer for the promotion of the oxidative hydroxylation of arylboronic acids under green light in the aqueous solution, giving a high yield of 91%. The present study not only presents a compelling illustration of photocatalysis utilizing a 2D SOF derived from triphenylamine, but also unveils promising avenues for the photocatalytic oxidation of SOF employing low-energy light systems. [ABSTRACT FROM AUTHOR]