Unusual Behavior of Donor–Acceptor Stenhouse Adducts in Confined Space of a Water-Soluble PdII8 Molecular Vessel

Abstract

Donor-Acceptor Stenhouse Adducts (DASA) are new generation photochromic compounds discovered in recent past. DASA exist normally in open form (blue/violet) and readily convert to cyclic (light yellow/colourless) zwitterionic form reversibly in presence of green light in toluene/dioxane. In aqueous medium, the open form is not stable and converts to the cyclic zwit-terionic form irreversibly. We report here a new self-assembled Pd8 molecular vessel (MV) that can stabilize and store the open form of DASA even in aqueous medium. Reaction of 90° acceptor cis-(tmeda)Pd(NO3)2 (M) [tmeda = N,N,N′,N′-tetramethylethane-1,2-diamine] with a symmetric tetraimidazole donor (L, 3,3',5,5'-tetra(1H-imidazol-1-yl)-1,1'-biphenyl) in 2:1 molar ratio yielded a water soluble [8+4] self-assembled M8L4 molecular barrel (MV). This barrel (MV) is found to be a potential molecular vessel to store and stabilize the open forms of DASA in aqueous medium over the more stable zwitteri-onic cyclic form, while in absence of the barrel the same DASA exist in cyclic zwitterionic form in aqueous medium. The hydrophobic interaction between the cavity and the open-form of DASA molecules benefits to reach an out of equilibrium or reverse equilibrium state in aqueous medium. Presence of excess molecular vessel (MV) could even drive the conversion of stable cyclic form to open form in aqueous medium. The host-guest complex is stable upon irradiating with green light. To the best of our knowledge, this is the first successful attempt to stabilize the open form of DASA molecules in aqueous me-dium and the first report on the fate of DASA in confined space discrete molecular architecture. Furthermore, the molecular vessel has been utilized for catalytic Michael addition reactions of a series of nitrostyrene derivatives with 1,3-indandione in aqueous medium.