New Sensitive and Selective Chemical Sensors for Ni²⁺ and Cu²⁺ Ions: Insights into the Sensing Mechanism through DFT Methods

We report the synthesis and theoretical study of two new colorimetric chemosensors with special selectivity and sensitivity to Ni²⁺ and Cu²⁺ ions over other metal cations in the CH₃CN/H₂O solution. Compounds (E)-4-((2-nitrophenyl)diazenyl)-N,N-bis(pyridin-2-ylmethyl)aniline (A) and (E)-4-((3-nitrophenyl)diazenyl)-N,N-bis(pyridin-2-ylmethyl)aniline (B) exhibited a drastic color change from yellow to colorless, which allows the detection of the mentioned metal cations through different techniques. The interaction of sensors with these metal ions induced a new absorption band with a hypsochromic shift to the characteristic signal of the free sensors. A theoretical study via time-dependent density functional theory (TD-DFT) was performed. This method has enabled us to reproduce the hypsochromic shift in the maximum UV-vis absorption band and explain the selective sensing of the ions. For all of the systems studied, the absorption band is characterized by a π → π* transition centered in the ligand. Instead of Ni²⁺ and Cu²⁺ ions, the transition is set toward the σ* molecular orbital with a strong contribution of the 3d²-² transition (π → 3d²-²). These absorptions imply a ligand-to-metal charge transfer (LMCT) mechanism that results in the hypsochromic shift in the absorption band of these systems.