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We present the results of dielectric measurements for three sizable glass-formers with identical nonpolar cores linked to various dipole-labeled rotors that shed new light on the picture of reorientation of anisotropic systems with significant moment of inertia revealed by broadband dielectric spectroscopy. The dynamics of sizable glass-formers formed by partially rigid molecular cores linked to small polar rotors in many respects differs from that of typical glass-formers. For instance, the extraordinarily large prefactors (τ 0  > 10 –12  s) in the Vogel–Fulcher–Tammann equation were found. The rich and highly diverse relaxation pattern was governed by the location of a dipole, its ability to rotate freely, and the degree of coupling to the motion of the entire sizable system.

Complex Reorientation Dynamics of Sizable Glass-Formers with Polar Rotors Revealed by Dielectric Spectroscopy