Selective Luminescent Chemosensing of Chloride Based on a Cyclometalated Platinum(II) Complex in Water: Crystal Structures, Spectroscopic Studies, Extraction, and Bioimaging.

Selective anion sensing by luminescent chemosensors capable of operating in aqueous conditions is a central field of modern supramolecular chemistry that impacts analytical and biological chemistry. A cationic cyclometalated [Pt(N^C^N)NCCH]OTf complex, [N^C^N = 1,3-bis(1-(-tolyl)-benzimidazol-2'-yl)benzene, OTf = triflate], was prepared, structurally described by single-crystal X-ray diffraction and studied in-depth as a luminescent chemosensor for anions in aqueous phase and solid state. A series of related neutral [Pt(N^C^N)X] complexes (X = Cl, ; CN, and I, ) were formed readily upon treatment of with the respective NaX salt in aqueous media and were described structurally by X-ray diffraction. Complex is hydrostable with phosphorescent green emission originated by intraligand transitions, and [d(Pt) → π*(N^C^N)] charge transfer transitions, as evidenced by TD-DFT calculations and lifetime. Additions of halides, pseudohalides, oxyanions, and dicarboxylates to a neutral aqueous solution of modified its green emission intensity with a pronounced affinity ( = 1.5 × 10 M) and turn-on signal toward Cl within the micromolar concentration range. Pt complex is two orders of magnitude more selective for Cl than the other halides, CN and basic oxyanions. Such Cl affinity for a metal-based chemosensor in aqueous media is still rare. On the basis of X-ray crystallographic analysis and multiple spectroscopic tools (NMR, UV-vis, luminescence, MS, lifetimes) the origin of this selectivity hinges on the cooperative three-point recognition involving one coordination bond (Pt-Cl) and two convergent short C-H···Cl contacts. This strong affinity and efficient optical response can be utilized in quantitative Cl sensing in real samples and solid-liquid extractions. Additionally, chloro-Pt complex, may be relevant to bioimaging as a marker for cell nuclei, as revealed by its emission within living cells and intracellular distribution by confocal microscopic studies. These results demonstrate the usefulness of the new water-stable luminescent Pt-N^C^N complexes as effective analytical tools in anion sensing and extraction agents.