Solvatochromic Effects of Reichardt’s Dyes and 4-[[(2,4-dinitrophenyl)methylene]imino-2,6-diphenyl]phenol in Individual Solvents and Aqueous-Organic Mixtures: Structural Features of Aqueous Solvents of Non-Electrolytes
Abstract
The solvatochromic effects of 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (Ind 1) and 4-[[2,4-dinitrophenyl)methylene]imino-2,6-diphenyl]phenol (Ind 2) were studied in 28 individual solvents and in 16 binary aqueous-organic mixtures.
It was found that in individual solvents, Ind 1 and Ind 2 show approximately the same nature in of the change in the solvatochromic effects when passing from one solvent to another, with the exception of water, in which Ind 2 shows an anomalously small solvatochromic effect, as compared with Ind 1. This anomaly is due to the fact that water can stabilize the excited state of Ind 2 because of hydration, while in Ind 1, only the ground state is stabilized.
It was found that in binary aqueous-organic mixtures, Ind 1 is not very suitable for studying their solvating ability, while Ind 2 shows a specific feature – a sharp drop in ЕТ at a certain concentration to values characteristic of pure water. It was assumed that the constant value of ЕТ after a sharp drop is associated with the possible existence of a micro-heterogeneous structure of a binary mixture at these compositions with micro-areas of water, in which both the structural (H-bonds) and hydration properties of pure water are preserved.
The shard drop of ЕТ can be explained by the change in the hydration shell around the phenolate oxygen atom in the ground state at the maximum dependence on the hydration shell around the nitro fragment in the excited state, which is characteristic of pure water.
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