Amphiphilic Azo-Functionalized Polyhedral Oligomeric Silsesquioxane; Synthesis and Photo-Switched Efficient Phase Transfer via Host-Guest Encapsulation

A new amphiphilic azo-functionalized polyhedral oligomeric silsesquioxane (POSS) derivative was synthesized by functionalizing octa(3-aminopropyl)silsesquioxane (OAS-POSS) with 4-((4-(dodecyloxy)phenyl)diazenyl)benzoic acid, affording a hydrophilic amino POSS head and hydrophobic dodecyl tail with a diphenyl-azo connector. Prepared amphiphilic azo-functionalized POSS (azo-POSS) exhibited high ability for encapsulation and transferring cationic dyes into the organic phase by vigorously mixing with aqueous solutions of each dye. The photo-controlled encapsulating properties of the synthesized phase transfer reagent was studied using cationic dyes, such as methylene blue (MB), crystal violet (CV) and thymol blue in acidic conditions. Results showed more than 95 % encapsulation of MB. However, no considerable encapsulation was shown in the case of anionic dyes such as eriochrome black T (EBT) and thymol blue in alkaline solutions. By trans/cis isomerization of the azo moiety of the phase transfer reagent by UV irradiation (365 nm), the amount of dye encapsulation was decreased, which could be attributed to the formation of cis isomer that led to the folding of the dodecyl alkyl tail on the POSS moiety, and therefore prevent to lay the 3-aminopropyl moieties of POSS head to the water/DCM interface to adsorb and encapsulate MB molecules. Amphiphilic azo-functionalized polyhedral oligomeric silsesquioxane (azo-POSS) possessing a hydrophilic amino head and hydrophobic dodecyl tail with a diphenyl-azo connector, exhibit high ability for encapsulation and transferring cationic dyes from aqueous into the organic phase.image