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1<i>H</i>-Imidazole derivatives establish one of the iconic classes of ESIPT-capable compounds (ESIPT = excited state intramolecular proton transfer). This work presents the synthesis of 1-hydroxy-4-(2-hydroxyphenyl)-5-methyl-2-(pyridin-2-yl)-1<i>H</i>-imidazole (<b>L^OH,OH</b>) as the first example of ESIPT-capable imidazole derivatives wherein the imidazole moiety simultaneously acts as a proton acceptor and a proton donor. The reaction of <b>L^OH,OH</b> with chloroacetone leads to the selective reduction of the imidazolic OH group (whereas the phenolic OH group remains unaffected) and to the isolation of 4-(2-hydroxyphenyl)-5-methyl-2-(pyridin-2-yl)-1<i>H</i>-imidazole (<b>L^H,OH</b>), a monohydroxy congener of <b>L^OH,OH</b>. Both <b>L^OH,OH</b> and <b>L^H,OH</b> demonstrate luminescence in the solid state. The number of OH···N proton transfer sites in these compounds (one for <b>L^H,OH</b> and two for <b>L^OH,OH</b>) strongly affects the luminescence mechanism and color of the emission: <b>L^H,OH</b> emits in the light green region, whereas <b>L^OH,OH</b> luminesces in the orange region. According to joint experimental and theoretical studies, the main emission pathway of both compounds is associated with T₁ → S₀ phosphorescence and not related to ESIPT. At the same time, <b>L^OH,OH</b> also exhibits S₁ → S₀ fluorescence associated with ESIPT with one proton transferred from the hydroxyimidazole moiety to the pyridine moiety, which is not possible for <b>L^H,OH</b> due to the absence of the hydroxy group in the imidazole moiety.