Excimer Formation Dynamics of Dipyrenyldecane in Structurally Different Ionic Liquids.

Ionic liquids, being composed of ions alone, may offer alternative pathways for molecular aggregation. These pathways could be controlled by the chemical structure of the cation and the anion of the ionic liquids. Intramolecular excimer formation dynamics of a bifluorophoric probe, 1,3-bis(1-pyrenyl)decane [1Py(10)1Py], where the fluorophoric pyrene moieties are separated by a long decyl chain, is investigated in seven different ionic liquids in 10-90 °C temperature range. The long alkyl separator allows for ample interaction with the solubilizing milieu prior to the formation of the excimer. The ionic liquids are composed of two sets, one having four ionic liquids of 1-butyl-3-methylimidazolium cation ([bmim+]) with different anions and the other having four ionic liquids of bis(trifluoromethylsulfonyl)imide anion ([Tf2N-]) with different cations. The excimer-to-monomer emission intensity ratio (IE/IM) is found to increase with increasing temperature in sigmoidal fashion. Chemical structure of the ionic liquid controls the excimer formation efficiency, as IE/IM values within ionic liquids with the same viscosities are found to be significantly different. The excited-state intensity decay kinetics of 1Py(10)1Py in ionic liquids do not adhere to a simplistic Birk's scheme, where only one excimer conformer forms after excitation. The apparent rate constants of excimer formation (ka) in highly viscous ionic liquids are an order of magnitude lower than those reported in organic solvents. In general, the higher the viscosity of the ionic liquid, the more sensitive is the ka to the temperature with higher activation energy, Ea. The trend in Ea is found to be similar to that for activation energy of the viscous flow (Ea,η). Stokes-Einstein relationship is not followed in [bmim+] ionic liquids; however, with the exception of [choline][Tf2N], it is found to be followed in [Tf2N-] ionic liquids suggesting the cyclization dynamics of 1Py(10)1Py to be diffusion-controlled and to depend on the viscosity of the ionic liquid irrespective of the identity of the cation. The dependence of ionic liquid structure on cyclization dynamics to form intramolecular excimer is amply highlighted.