Conjugated porous polymers with narrow bandgaps, tunable morphologies, porosities and optoelectronic properties are synthesized via facile direct arylation polymerization.

Conjugated microporous polymers are synthesized via facile direct arylation polymerization, resulting in conjugated networks with hierarchical porosity and a narrow bandgap of 1.5 eV.

Direct arylation polymerization (DAP) enabled facile synthesis of a narrow bandgap donor–acceptor conjugated polymer (PDFBT‐Th4) composed of alternating 5,6‐difluoro‐2,1,3‐benzothiadiazole and alkyl‐quaternarythiophene. The optimized reaction condition of DAP catalyzed with Pd(OAc)2/(o‐MeOPh)3P/PivOH/K2CO3 in o‐xylene led to the target polymer with a number‐average molecular weight (Mn) of 14.6 kDa without noticeable homocoupling or β‐branching defects. UV‐vis absorption spectra of PDFBT‐Th4 indicate strong interchain aggregation in films. While the C‐H selectivity and the alternating polymer structure of PDFBT‐Th4 synthesized via DAP are comparable to those of the same type polymers synthesized via Stille coupling, the batch of PDFBT‐Th4 synthesized via optimal DAP, despite its lower Mn, showed higher hole mobility in field effect transistors and larger power conversion efficiency in organic solar cell devices. These results further demonstrate the promising potential of DAP for efficient synthesis of high‐performance D‐A conjugated polymers for broad optoelectronic applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1869–1879

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