Organic π-conjugated polymers and small molecules, featured by low cost, light weight, solution processibility as well as finely adjustable structure and properties, have become kinds of fundamental semiconductor materials for next generation of optoelectric devices. The C——B/C——X Suzuki and C——Sn/C——X Stille couplings have become the most widely used strategy for the construction of sp²-C——C bonds involved in organic semiconductor materials. However, these traditional C——C coupling reactions usually involve prefunctionalization of subtrates and multipe synthetic steps, along with toxic by-products. In recent years, the direct C——H arylation reaction (C——H/C——X coupling) for the construction of sp²-C——C bonds and the synthesis of organic π-conjugated materials, featured by the simplicity without use of organometallic precursors, high atom- and step-econogy and low cost, has attracted extensive attention from researchers, due to its great potential for pratical applictions. The C——H/C——X direct arylation coupling has great potential in the efficient synthesis and practical application of organic optoelectric materials. Herein, an overview of recent developments in direct C——H arylation for the synthesis of organic conjugated functional materials used in device applications is provided, including organic photovoltaics (OPV), organic field effect transistor (OFET), dye-sensitized solar cell (DSSC), perovskite cells (PSC), organic light emitting diode (OLED) and lithium rattery, etc. The advantages, challenges as well as the future developments in the area of direct C——H arylation are also discussed and commented.

Key words: direct C—H arylation, π-conjugated functional materials, atom- and step-economic synthesis, organic solar cells, organic field effect transitors, organic optoelectric devices