Flexible and UV Resistant Films Based on Thiophene‐Substituted Conjugated Microporous Polymers Bearing Alkyl Chains: Tuning of Rigidity into Soft

Abstract Conjugated microporous polymers (CMPs) are usually formed as rigid π‐conjugated networks and insoluble in common solutions which in turn have limitations in molding or process for applications due to its unprocessability. In this work, a series of CMPs containing thiophene‐moieties (SCMPs) are obtained by dibromothiophene with carbon branched chain and ethynylbenzene monomers. The solubility of the SCMPs would be significantly improved by tuning the length of alkyl chains in alkyl‐substituted dibromothiophene monomers. SCMPs products bearing different alkyl‐substituted dibromothiophene moiety exhibit an interesting transition from insolubility to solubility in most common organic solvents, which would greatly improve its processability. Taking advantage of its solubility, freestanding SCMPs films and flexible and transparent UV resistant PDMS films based on SCMPs coatings can be easily fabricated by simple coating methods. These finding may provide a possibility for future design and fabrication of soluble and processable CMPs by rational design and tuning alkyl‐substituted aromatic monomers.