Encapsulation and Stabilization of a Donor-Acceptor Stenhouse Adduct Isomer in Water Inside the Blue Box: A Combined Experimental and Theoretical Approach.

Abstract

We synthesized two types of donor-acceptor Stenhouse adducts (DASAs), a new type of photochromic molecules showing dual color in two different isomeric forms in solution phase, using Meldrum acid (DASA-Mel) and barbituric acid (DASA-Bar), along with a naphthalimide derivative to obtain interesting fluorescence properties. DASA-Mel was found to have fast photochromic conversion in comparison to DASA-Bar, evident from ultraviolet-visible (UV-vis) and fluorescence spectroscopic studies. The colored form of DASA-Mel was encapsulated inside the water-soluble Stoddart's blue box and became soluble in water much faster than DASA-Bar. Interestingly, the competitive encapsulation experiment showed that DASA-Mel was selectively encapsulated inside the blue box in water whereas DASA-Bar was mostly separated out from the solution after centrifugation, and this phenomenon was confirmed by 1H and DOSY NMR and mass spectroscopies. Moreover, we found through density functional theory (DFT) optimization that the open form of DASA-Mel was more stable during the encapsulation reaction in a water medium in comparison to DASA-Bar. The calculated binding energies of encapsulated DASA-Mel and DASA-Bar are -10.2 and -9.9 kcal/mol, respectively, clearly showing that the former is more stable by 0.3 kcal. Consequently, the organic macrocycle selectively separating one kind of DASA from a mixture by encapsulation in water is reported for the first time with experimental and theoretical support in the literature.