Methods of synthesis and application thereof for peripherally aromatic silsesquioxanes featuring reactive functionality. A method, according to one embodiment of the invention, includes reacting a polyhedral oligomeric silsesquioxane with an anhydride. The polyhedral oligomeric silsesquioxane has an inorganic core, a phenyl moiety or an anlyine moiety covalently coupled to the at least one T-type silicon atom; and a metal-aniline group or a para-aniline group covalently coupled to the at least one D-type or M-type silicon atom. The inorganic core includes 6-14 silicon atoms, at least one of the silicon atoms being an M-type silicon atom or a D-type silicon atom, and at least one of the silicon atoms being a T-type silicon atom, and 9-20 oxygen atoms.
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