Direct (hetero)arylation polymerizations (DHAP) have attracted great attention in recent years to synthesize various conjugated polymers such as polythiophenes and polycarbazoles. DHAPs can reduce undesired organometallic byproducts and the number of synthetic steps. However, conventional DHAPs are limited to C-C bond formation, and polymerization method for C-N bond formation using C-H activation has remained unexplored to date. Here, we report a Iridium-catalyzed Direct C-H amidation polymerization (DCAP) that enables the synthesis of high-molecular-weight and defect-free polysulfonylamides. We discovered that a reactive directing group, additives, silver salts, and reaction temperature were key factors for efficient DCAP through model study and optimization. This polymerization allowed high-molecular-weight polysulfonylamides with various readily accessible bis-sulfonyl azides. Furthermore, synthesized polymers emited fluorescence with high quantum yields and large stokes shifts due to excited-state intramolecular proton transfer (ESIPT) without conjugated moieties like conventional fluorescent conjugated polymers. Notably, this research demonstrates a successful atom- and step-economical DCAP showing defect-free and high-molecular-weight fluorescent polysulfonylamides.

Direct C-H amidation polymerization forming C-N bond for fluorescent polysulfonylamides using iridium catalyst

254th National Meeting (2017)

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