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A photocontrolled reversible addition−fragmentation chain transfer (RAFT) process is developed by initiating polymerization through a 1,3‐diaminopropane‐triethylborane (DAPTB)−diphenyl iodonium salt (Ph2I+) complex (DAPTB/Ph2I+) under ambient temperature and atmospheric conditions. Upon demand, this air‐stable DAPTB/Ph2I+ complex is photolyzed to liberate a reactive triethylborane that consumes atmospheric...
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