Stimuli-Responsive Molecular Switches and Logic Devices Based on Ru(II)-Terpyridyl-Imidazole Coordination Motif

We report herein the synthesis, photophysics, and electrochemistry of three Ru(II)-terpyridine complexes derived from a new terpyridyl-imidazole ligand (tpy-HImzPhF) and study their pH- and temperature-responsive behaviors toward the fabrication of molecular switches. The complexes emitted at room temperature (RT) have a lifetime within the 4.5-49.0 ns domain, depending on the auxiliary ligand and the solvent used. In the acidic region, the complexes exhibit emission, indicating the "on-state", while in the basic condition, the emission is totally quenched, indicating the "off-state". Similarly, when the temperature is lowered, the emission intensity and lifetime are enhanced, demonstrating the on-state, while increase of temperature leads to quenching of the emission intensity and lifetime, designated as the off-state. In both cases, the process is reversible. The bathochromic shift of the spectral band together with the emission quenching and lowering of the Ru³⁺/Ru²⁺ potential is also observed upon deprotonation at elevated pH. In addition, systematic variation of the absorption spectral behaviors upon variation of pH helps in evaluation of the pK_a's of the complexes. In essence, the complexes can act as switches emanated from a huge change in their absorption, emission, and redox behaviors as a function of their acidity/basicity (pH) and temperature. Moreover, their emission spectral responses as a function of pH and temperature were utilized for the fabrication of two-input binary logic gates. Density-functional theory (DFT) and time-dependent density-functional theory (TD-DFT) computations are performed for appropriate interpretation of the spectral bands.