Phototransients of 2-ethylaminodiphenylborinate generated by direct photolysis and photosensitization ☆
Ground state interactions and excited states and transients formed after photolysis and photosensitization of 2-ethylaminodiphenylborinate (2APB) were studied by various techniques. The UV spectrum shows a large absorption band at 235 nm (ɛ = 14,500 M−1 cm−1) with a shoulder at 260 nm. The fluorescence spectra show increasing emission intensity with maximum at 300 nm, which shifts to the red up to 10−3 M concentrations. At higher concentrations, the emission intensity decreases, probably due to the formation of aggregates. UV excitation in deareated solutions shows the formation of two transients at 300 and 360 nm. The latter has a lifetime of 5.7 μs in ethanol and is totally quenched in the presence of oxygen and assigned to the triplet state of 2APB. The 300 nm peak is not affected by oxygen, has a lifetime in the order of milliseconds, and corresponds to a boron-centered radical species originated from the singlet state. A boron radical can also be obtained by electron transfer from triplet Safranine to the borinate (kq = 9.7 × 107 M−1 s−1) forming the semioxidized form of the dye. EPR experiments using DMPO show that dye-sensitized and direct UV-photolysis of 2ABP renders initially arylboron-centered radicals.
Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► The photolysis and photosensitization of 2-ethylaminodiphenylborinate (2APB) was studied. ► Boron-centered radicals were formed in both cases. ► Direct UV photolysis formed a short-lived triplet (μs) and a long-lived radical (ms). ► 2APB quenched the triplet of Safranine forming a boron radical. ► 2ADP can be used as polymerization photoinitiator or co-initiator.
Journal: Journal of Photochemistry and Photobiology A: Chemistry - Volume 236, 15 May 2012, Pages 14–20