Aryl radical initiators accumulated within layered silicates realize polystyrene with directly and regioselectively bonded aryl-terminal groups.

The arbitrary design of a terminal group of polymers exploits the still-veiled functions of polymers with potential for application in fields such as drug delivery systems, photonics, and energy conversions. Here we demonstrate for the first time that polystyrenes with directly and regioselectively bonded aryl-terminal groups can be obtained via styrene radical polymerization initialized by arbitrary aryl radicals accumulated within the interlayer space of smectite clay minerals, which can be prepared by our developed ‘Clay Catalysed ab intra Deamination (CCD)’ method.