High pressure optical studies of crystalline anils and related compounds

Abstract

High pressure optical studies have been made on a series of crystalline therochromic and photochromic anils and model compounds. Measurements include absorption and emission peak locations and the integrated intensities of various absorption peaks including the uv peak and visible peaks introduced thermally or by irradiation at various temperatures and pressures. Emission yields were also obtained. For the thermochromic compounds there was a large increase in the equilibrium yield of the thermally induced peak with pressure (piezochromism), corresponding to a volume decrease of ∼1.2 cc/mole for 5-bromosalicylidene aniline (5BrSA). The emission peak shifts to lower energy and decreases in intensity primarily because of increased rate of the radiationless conversion. For salicylidene aniline and related photochromic crystals the rate of photochromic conversion varied with both pressure and temperature in a manner which depends on the size of the energy barriers to the forward and reverse processes. The emission yield increases with pressure at low pressure, goes through a maximum, and decreases at high pressure. At low pressure the dominant feature is increase in occupation of the emitting state while at high pressure the increased rate of the radiationless process governs. For 2- (O-hydroxyphenyl) benzoxazole (OHBO) (see Fig. 1), where a keto–enol rearrangement is most probable, the changes in absorption and emission intensity can be related to the same diagram used for the anils. This diagram also describes the behavior of benzilidene aniline (BA), where only a cis–trans isomerization is possible.