Design, Synthesis, and Characterizations of a Series of Pt₄ Macrocycles and Fluorescent Sensing of Fe³⁺/Cu²⁺/Ni²⁺ Through Metal Coordination

Abstract

A PtII2 organometallic “clip” (1a) containing ethynyl functionality is synthesized. Multinuclear NMR and electrospray ionization mass spectrometry characterized this “clip”, and the molecular structure was determined in an X-ray single-crystal diffraction study. A series of discrete molecular rectangles (2a−d) have been synthesized from this “clip” in combination with dipyridyl-based linear linkers (L1−4) by a metal−ligand coordination driven self-assembly approach [where L1 = 4,4′-bipyridine, L2 = trans-1,2-bis(4-pyridyl)ethylene, L3 = N-(4-pyridyl)isonicotinamide, and L4 = N,N′-bis(4-pyridylidene)ethylenediamine]. Rectangle 2d was designed using the imine-based ligand L4 to make it a system composed of a fluorophore−receptor−fluorophore combination. The imine N4 pocket is the receptor site, while the anthracene-based “clip” is the fluorophore. Complex 2d is fluorescent in nature and showed fluorescence quenching in solution upon the binding of hard transition metal ions (Fe3+, Cu2+, Ni2+, and Mn2+) into the N4 pocket. The nonresponsive nature of the fluorescence intensity upon the addition of soft metal ions (Zn2+ and Cd2+) having d10 configuration makes it a suitable sensor for transition metal ions. The fluorescence intensity of the Ni2+ bound complex was regained when the metal was removed by a stronger chelating 2,2′-dipyridyl ligand