CO2‐Fueled Transient Breathing Nanogels that Couple Nonequilibrium Catalytic Polymerization

Abstract Here we present a “breathing” nanogel that is fueled by CO 2 gas to perform temporally programmable catalytic polymerization. The nanogel is composed of common frustrated Lewis pair polymers (FLPs). Dynamic CO 2 ‐FLP gas‐bridging bonds endow the nanogel with a transient volume contraction, and the resulting proximal effect of bound FLPs unlocks its catalytic capacity toward CO 2 . Reverse gas depletion via a CO 2 ‐participated polymerization can induce a reverse nanogel expansion, which shuts down the catalytic activity. Control of external factors (fuel level, temperature or additives) can regulate the breathing period, amplitude and lifecycle, so as to affect the catalytic polymerization. Moreover, editing the nanogel breathing procedure can sequentially evoke the copolymerization of CO 2 with different epoxide monomers preloaded therein, which allows to obtain block‐tunable copolycarbonates that are unachievable by other methods. This synthetic dissipative system would be function as a prototype of gas‐driven nanosynthesizer.