Calculation driven synthesis of an excellent dihydropyrene negative photochrome and its photochemical properties

Abstract

The photochromic properties of dihydropyrenes have been substantially improved by making use of density functional theory (DFT) activation barrier calculations, which suggested that the di-isobutenylcyclophanediene 15′ should have a significant barrier to thermal isomerization to the dihydropyrene (DHP) 15, which itself should resist isomerization involving migration of the internal groups to the rearranged dihydropyrene 9 (X = -CH=C(Me)2). As a result of these calculations, the synthesis of the colorless cyclophanediene (CPD) 15′ was undertaken and achieved from the dinitrile 28 in four steps in 37% overall yield %. The cyclophanediene 15′ thermally isomerized to the dihydropyrene 15 at 100 °C with t1/2 = 4.5 h, giving an extrapolated 20 °C t1/2 of ∼16 y, consistent with the DFT calculations. No evidence for [1,5]-sigmatropic rearrangement in to 9 (X = -CH=C(Me)2) was observed on heating to 130 °C. The ring-opening isomerization quantum yields (βopen) for DHP 15 in to CPD 15′ were determined in cyclohexane to be 0.12 ± 0.01, which is three times greater than for the benzoDHP 1. Friedel-Crafts naphthoylation of 15 gave 70% of purple 32, which in toluene showed the largest photochemical ring-opening isomerization quantum yields (βopen) of 0.66 ± 0.02 for any known dihydropyrene, ∼nine times greater than 1 in toluene. The thermal closing of 32′ to 32, although faster than for 15′, gave a useful extrapolated t1/2 of ∼2 y at 20 °C. © 2011 American Chemical Society.