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Our investigations on 100 SMs in (plasticized) PVP films reveal a wide distribution of dwell times and pause frequencies, demonstrating that most probes intermittently experience complete translational and rotational immobilization. This indicates that tracers serendipitously encounter compact, rigid polymer cavities during transport, implying the existence of nanoscale glass-like domains sparsely distributed in a predominantly deep-rubbery polymer network far above the glass transition.A series of ionic liquids based on the 1-alkyl-3-m