Stereospecific Formation of the rctt Isomer of Bis-crown-Containing Cyclobutane upon [2 + 2] Photocycloaddition of an (18-Crown-6)stilbene Induced by Self-Assembly via Hydrogen Bonding

The formation and the spectroscopic and structural properties of 1:1 and 2:1 (ligand-to-dication) complexes of an (18-crown-6)stilbene with ethane-1,2-diammonium diperchlorate in MeCN were studied by UV–vis and NMR spectroscopy and by density functional theory calculations. Prolonged UV irradiation of 2:1 mixtures of the crown stilbene and the diammonium salt led to the formation of two main photoproducts, namely, the single syn-“head-to-head” photodimer of the crown stilbene (rctt cyclobutane) due to supramolecular-assisted [2 + 2] photocycloaddition and a crown ether derivative of phenanthrene due to a photoinduced electrocyclization reaction. The rctt cyclobutane was isolated by preparative photolysis, followed by chromatography. The selectivity of the [2 + 2] photocycloaddition is explained by supramolecular pre-organization of crown stilbene molecules into the 2:1 complexes that have a pseudo-sandwich structure with stacking interactions between the stilbene moieties.