Synthesis of triptycene-derived covalent organic polymer networks and their subsequent in-situ functionalization with 1,2-dicarbonyl substituents

Three-dimensional polymer derivatives TP1-4 containing triptycene comonomers were synthesized from 1,4-diethynyl triptycene 1 with various di-, tri-, and tetra-brominated aromatic building blocks 3a-d through the mild Sonogashira cross-coupling reaction conditions. The abovementioned alkyne-containing copolymers were subsequently oxidized into their respective 1,2-diketone derivatives, OTP1-4, under mild reaction conditions. The UV-Vis and emission studies of copolymers TP1-4 and their oxidized homologues OTP1-4 confirmed the major influence of the aromatic substituent on the copolymer conjugation. Thermogravimetric analysis of copolymers TP1-4 revealed relatively high 10% weight loss temperature values (T-d) reaching up to 490 degrees C. On the other hand, the 1,2-diketone containing target polymers OTP1-4 showed lower 10% weight loss temperature values T-d, with a maximum of 431 degrees C.