Stimuli-Responsive Near-Infrared Emissive Os(II)-Terpyridine Complexes with a Sense of Logic

Two bis-tridentate Os(II) compounds based on a heteroditopic terpyridine-bipyridine-type ligand were synthesized, and their photophysical properties were thoroughly studied. The compounds exhibit strong spin-allowed ¹MLCT bands in the visible domain (489-521 nm) as well as weak ¹GS to ³MLCT bands within the 668-815 nm domain. The compounds display strong luminescence from the ³MLCT state in the near-infrared domain (728-780 nm) at room temperature having lifetimes in the range of 20.0-171.0 ns. After coordination of [Os(tpy-PhCH₃/H₂pbbzim)₂]²⁺ unit to the terpyridine site of tpy-Hbzim-dipy, the complexes offer vacant pyridine-imidazole motifs for interacting with cationic and anionic guests. Consequently, photophysical properties of the compounds were tuned to a great extent upon interaction with selected cations, anions, pH, as well as protons. Anion-induced alteration of the ground- and excited-state properties of the compound lead to recognition of specific anions in solution. Significant change in the optical spectral behaviors as well as switching of emission spectral properties of the compounds was done in the NIR region upon treating with anions, cations, protons, and solvents (dichloromethane, acetonitrile, methanol, dimethylsulfoxide, and water). Moreover, the optical outputs in response to external stimuli were used to demonstrate binary functions of two-input IMPLICATION, NOR, and XNOR logic gates.