Light-induced selectivity in an exemplary photodimerization reaction of varied azaanthracenes

Currently, there is intense interest in light-driven chemical reactions, including photocatalytic processes, photopolymerization and photodimerization. The need for regiocontrol in such reactions is obvious, especially in cases where many products can potentially be formed. Here, the photodimerization involving various azaanthracenes is presented for the first time. Specifically, 2-azaanthracene (A) and N-methyl-2-azaanthracene (M) are considered. Photoreactions of A, M and the A + M mixture under two irradiation wavelengths (365 and 420 nm) and in two solvents (methanol, dichloromethane) were carried out. In the case of A, four regiomers were obtained, in contrast to the available literature data, where only two products were reported. The relative ratio of these products is a function of the irradiation wavelength, the solvent used, and the irradiation time. In the case of M, we have identified two main products and a small amount of a third one, again contradicting the literature data. Irradiation of an equimolar A and M mixture at 365 nm led to a mixture of several products, where the yield of the AM dimers was about 40%. Importantly, the change of the irradiation wavelength to 420 nm significantly increased the AM yield (to about 80%). We demonstrated that only two AM dimers were formed (out of a possible four). The products were comprehensively characterized by NMR spectroscopy. We have determined the photophysical parameters of A and M and measured the quantum yield of photodimerization using UV-vis spectroscopy. The quantum-chemical calculations in the excited state allowed us to propose a plausible explanation for why only two AM dimers are formed upon irradiation. The presented results indicated that photodimerization among various molecules can have advantages and, in particular, does not need to give a complex mixture of multiple products. Importantly, it has been observed that the wavelength shift can significantly improve the photoreaction selectivity.