Controlled self-assembly of bis(crown)stilbenes into unusual bis-sandwich complexes: structure and stereoselective [2+2] photocycloaddition

Abstract

It was shown by ¹H NMR spectroscopy that symmetrical bis(crown)stilbenes (L) and small alkali and alkaline-earth metal cations form 1(L) ∶ 1(M^m+) and 1(L) ∶ 2(M^m+) complexes in MeCN solutions. In the case of large or hydrated metal cations such as Cs⁺, Rb⁺, K⁺, Ba²⁺, Sr²⁺, [Ca(H₂O)_x]²⁺ and stilbenes with a small crown-ether cavity as compared with the metal cation size, stable bis-sandwich complexes 2(L) ∶ 2(M^m+) can also be formed. A stable bis-pseudosandwich 2 ∶ 2 complex is also produced from bis(18-crown-6)stilbene with the propanediammonium ion. The effect of the crown-ether size and the cation size and nature on the route of stilbene phototransformation and product composition was elucidated. The bis-(pseudo)sandwich complexes undergo effective stereoselective [2+2] photocycloaddition giving mainly rctt isomers of new 1,2,3,4-tetracrown cyclobutanes. The structures of complexes of bis(crown)stilbenes and obtained cyclobutanes were confirmed by X-ray diffraction.