Volkov M Yu, Sharipova A R, Turanova O A
Zavoisky Physical-Technical Institute, FRC Kazan Scientific Center of RAS, Kazan, Russia.
Photochem Photobiol Sci. 2024 Oct;23(10):1971-1981. doi: 10.1007/s43630-024-00646-y. Epub 2024 Oct 7.
Two azo dyes 2-hydroxy-5-(4-nitrophenylazo)benzaldehyde and 2-hydroxy-5-(4-chlorophenylazo)benzaldehyde dissolved in carbon tetrachloride, hexane, acetone and acetonitrile were irradiated with 365 nm UV light, and processes, occurring in them, were studied by NMR and UV-vis spectroscopy. It was established that reversible trans/cis photoisomerization of the molecules occurs in the non-polar solvents and is not observed in the polar solvents. 2D NOESY NMR spectroscopy was used to identify isomers of the azo compounds. Based on the chemical shifts of the signals, it was established that these compounds are in the trans-form before UV irradiation. Spectra of the azo dyes before and after UV irradiation allowed assignment of the chemical shifts of the cis-isomers. In polar solvents these compounds undergo a hypochromic effect under heating or irradiation with UV light. Both compounds exhibit solvatochromism. The shifts in NMR signals caused by photoisomerization of the molecules were compared with the shifts in the NMR signals of other azo compounds such as Disperse Orange 3, Disperse Red 1 and azobenzene.
将溶解于四氯化碳、己烷、丙酮和乙腈中的两种偶氮染料2-羟基-5-(4-硝基苯基偶氮)苯甲醛和2-羟基-5-(4-氯苯基偶氮)苯甲醛用365 nm紫外光照射,并通过核磁共振(NMR)和紫外可见光谱研究其中发生的过程。结果表明,分子的可逆反式/顺式光异构化在非极性溶剂中发生,而在极性溶剂中未观察到。二维核欧沃豪斯效应光谱(2D NOESY NMR)用于鉴定偶氮化合物的异构体。根据信号的化学位移确定,这些化合物在紫外光照射前为反式结构。紫外光照射前后偶氮染料的光谱可确定顺式异构体的化学位移。在极性溶剂中,这些化合物在加热或紫外光照射下会发生减色效应。两种化合物均表现出溶剂化显色现象。将分子光异构化引起的核磁共振信号位移与其他偶氮化合物(如分散橙3、分散红1和偶氮苯)的核磁共振信号位移进行了比较。