Donor-acceptor complex formation in tetra-n-butylammonium chloride: n-decanoic acid deep eutectic solvent

Complex formation between pyrene (Py) and N,N-dimethylaniline (DMA) is presented in a deep eutectic solvent constituting of tetra-n-butylammonium chloride (TBAC) and n-decanoic acid (DA) in a 1:2 mol ratio, respectively, named TBAC:DA. The addition of DMA to a Py solution of TBAC:DA results in the formation of a fluorescent Py-DMA charge-transfer complex, which is manifested via a broad structureless bathochromically shifted band centered at 550(±2) nm. The solvatochromic nature of the Py-DMA fluorescent complex indicates the solvent polarity of TBAC:DA to be higher than that of methanol. The absence of a negative pre-exponential factor in the intensity decay at 550 nm combined with the excitation scans implies the presence of weak interaction between Py and DMA in the ground-state, leading to the rapid formation of a Py-DMA complex possibly at a sub-nanosecond time scale. The Stern-Volmer quenching constant (K_SV) varies from 53(±2) to 96(±1) M^-1, and the bimolecular quenching rate constant (k_q) varies from 3.0(±0.4) × 10⁸ to 8.8(±1.3) × 10⁸ M^-1 s^-1 by increasing the temperature (T) from 283.15 to 313.15 K, implying efficient deactivation of electron-acceptor Py in the excited-state induced effectively by the electron-donor DMA within TBAC:DA. ln k_q varies linearly with 1/T with an activation energy (E_a) of 26.4(±0.4) kJ mol^-1. The linear behavior between k_q and 1/η suggests conformity to the Stokes-Einstein relationship within TBAC:DA. The Py-DMA complex formation efficiency increases with an increase in T and reaches maxima at 298.15 K before decreasing with a further increase in T. The initial reduction in η favors Py-DMA complex formation; this effect is overcome by preferential thermal deactivation of the Py-DMA fluorescent complex as compared to that of pyrene.