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Fluorescence anisotropy measurements and molecular dynamics (MD) simulations have been performed to understand the specific interactions of two structurally similar nondipolar solutes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP), with neat 1-butyl-3-methylimidazolium dicyanamide ([BMIM][N(CN)]) and also in the presence of glucose. It has been observed that the measured reorientation times of DMDPP in neat [BMIM][N(CN)] follow the predictions of the Stokes-Einstein-Debye hydrodynamic theory with slip boundary condition. Addition of glucose (0.075 and 0.15 mole fraction) has no bearing on the rotational diffusion of the solute apart from the viscosity related effects. In contrast, the reorientation times of DPP in neat [BMIM][N(CN)] obey stick boundary condition as the hydrogen bond donating solute experiences specific interactions with the dicyanamide anion. No influence of the additive can be noticed on the rotational diffusion of DPP at 0.075 mole fraction of glucose. However, at 0.15 mole fraction of glucose, the reorientation times of the solute at a given viscosity and temperature decrease by 15-40% compared to those obtained in the neat ionic liquid. MD simulations indicate that each DPP molecule hydrogen bonds with two dicyanamide anions in neat ionic liquid. The simulations also reveal that, at 0.15 mole fraction of glucose, the concentration of anions hydrogen bonded to glucose increases significantly; therefore, the percentage of solute molecules that can form hydrogen bonds with two dicyanamide anions decreases to 84, which leads to faster rotation of DPP.

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