Preparation and properties of novel cross-linked fluoroalkyl end-capped cooligomeric nanoparticles possessing double decker-type aromatic silsesquioxane segments as core units

Cross-linked fluoroalkyl end-capped cooligomers possessing double decker-type aromatic silsesquioxane segments as core units [R_F-(Ar-SiSQ) _x -(Co-M) _y -R_F] were prepared under mild conditions by the cooligomerizations of fluoroalkanoyl peroxide with the corresponding aromatic silsesquioxane possessing bifunctional vinyl groups (Ar-SiSQ) and comonomers (Co-M) such as acryloylmorpholine (ACMO), N,N-dimethylacrylamide (DMAA) and N-(1,1-dimethyl-3-oxobutyl)acrylamide (DOBAA). Interestingly, these cross-linked fluorinated cooligomers thus obtained were found to form the nanometer size-controlled nanoparticles with a good dispersibility in a variety of solvents including fluorinated aliphatic solvents. These fluorinated cooligomeric nanoparticles were demonstrated to have red-shifted fluorescent emissions related to the presence of aromatic silsesquioxane segments, compared with that of parent aromatic silsesquioxane, indicating that each aromatic moiety in these nanoparticles can interact effectively with each other through the π–π stacking between the aromatic moieties to afford the red-shifted fluorescent emissions. These fluorinated nanoparticles were also applied to the surface modification of poly(methyl methacrylate) (PMMA) to exhibit not only a good oleophobicity imparted by fluorine but also a fluorescent emission behavior related to aromatic silsesquioxane segments in nanoparticles on the modified PMMA surface. More interestingly, cross-linked R_F-(Ar-SiSQ) _x -(DOBAA) _y -R_F cooligomeric nanoparticles interacted with fluorescein to give the corresponding fluorinated cooligomeric particles/fluorescein nanocomposites in methanol. These fluorinated fluorescein nanocomposites were found to afford an extraordinarily enhanced light absorption (λ _max = 441 nm), compared with that of fluoroalkyl end-capped DOBAA oligomer [R_F-(DOBAA) _n -R_F] possessing no aromatic silsesquioxane segments.