Molecular motion of polycarbonate included in γ‐cyclodextrin

Molecular motions of single polycarbonate (PC) chains threaded into crystalline γ‐cyclodextrin (γ‐CD) channels were examined using solid‐state ¹³C NMR and molecular dynamics simulations. The location of PC within the channels was confirmed by spin diffusion from a PC ¹³C label to natural‐abundance ¹³C of the γ‐CD. Rotor‐encoded longitudinal magnetization (RELM) (under 7‐kHz magic‐angle sample‐spinning conditions) was combined with multiple‐pulse ¹H‐¹H dipolar decoupling to detect large‐amplitude phenyl‐ring motion in both bulk PC and polycarbonate γ‐cyclodextrin inclusion compound (PC‐γ‐CD). The RELM results indicate that the phenyl rings in PC‐γ‐CD undergo 180° flips faster than 10 kHz just as in bulk PC. The molecular dynamics simulations show that the frequency of the phenyl‐ring flips depends on the cooperative motions of PC atoms and neighboring atoms of the γ‐CD channel. The distribution of protonated aromatic‐carbon laboratory and rotating‐frame ¹³C spin‐lattice relaxation rates for bulk PC and PC‐γ‐CD are similar but not identical. The distributions for both systems arise from site heterogeneities. For bulk PC, the heterogeneity is attributed to variations in local chain packing, and for PC‐γ‐CD the heterogeneity arises from variations in the location of the PC phenyl rings in the γ‐CD channel. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1271–1282, 2007