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

Abstract

We report herein the synthesis, photophysics, and electrochemistry of three Ru(II)-terpyridine complexes derived from a new terpyridyl-imidazole ligand (tpy-HImzPh3F2) 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 pKa'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.