Anomalous Polymer Chain Dynamics Acceleration and Viscosity Reduction from the Complexation of Amphipathic Metal–Organic Polyhedra

The accelerated polymer dynamics in polymer nanocomposites (PNCs) is rarely reported and poorly understood mainly due to the poor dispersion of nanoparticles with repulsive interaction in the polymer matrix. Herein, 2 nm amphipathic metal-organic polyhedra (MOP) are applied to complex with poly(4-vinylpyridine) (P4VP) as a model system for the understanding of chain dynamic acceleration and viscosity reduction mechanism in PNCs. The MOP surface is precisely modified with six amine groups for hydrogen-bonding interaction with P4VP, ensuring the good dispersion of MOPs. Meanwhile, the MOP surface is dominated by the ferrocene group that disfavors the close packing with P4VP, and the repulsive interaction contributes to the significant reduction of the glass transition temperature by 21.5 K. The measured polymer chain relaxation rate is accelerated for 3 orders of magnitude after complexation, contributing to the significantly reduced elastic moduli and complex viscosity. Our study provides a microscopic understanding of the chain dynamic modulation mechanism in PNCs and paves new avenues for the design of novel PNCs with emergent functions.