where H is the enthalpy change of a reaction (herein the adsorption and desorption events, in J mol -1 ), S is the entropy change in J K -1 mol -1 , T is the temperature in K, and R is the gas constant (8.314 J K -1 mol -1 ). The van't Hoff plot for the homogeneous pair gave H of -34 kJ mol -1 and S of -8.4 J K -1 mol -1 (Fig. left). DFT calculation (Fig. ) corroborated the 1:1 binding of the homogeneous pair, as suggested by the Hill plot (Fig. ), with a computed Hcalcd value of -27 kJ mol -1 . On the contrary, the relationship for the heterogeneous "stronger" association showed a quasi-linear behavior with R 2 = 0.949 in a narrow temperature range, with H1 of -56 kJ mol -1 and S1 of -53 J K -1 mol -1 , respectively (Fig. right). For the heterogeneous pair, the sparse surface functionalization of 1 (0.09 per square nanometer, Table ) would support 1:1 binding even at the interfaces. As such, the larger heat of association at the interfaces (-56 kJ mol -1 ) compared with that for the homogeneous pair (-34 kJ mol -1 ) could be rationalized by the additional interactions with unobtrusive sites of the polymer units. In fact, the entropic contribution for the "stronger" binding (S1 = -53 J K -1 mol -1 ) was highly negative toward the association compared to the corresponding homogeneous molecular system (S = -8.4 J K -1 mol - 1 ), and could be rationalized by the conformational changes upon association with OTA. That is, the approach of OTA may cause the induced fit of poly1, and this requires an additional loss of conformational freedom within poly1, leading to a decrease in S1. This interpretation supported the polymer-assisted association of OTA with poly1.