Cd²⁺-Specific Fluorescence Response of Methoxy-Substituted <i>N</i>,<i>N</i>‑Bis(2-quinolylmethyl)-2-methoxyaniline Derivatives

The N3O1 tetradentate ligand, TriMeOBQMOA (N,N-bis(5,6,7-trimethoxy-2-quinolylmethyl)-2-methoxyaniline), was developed as a Cd2+-specific fluorescent sensor. The structure of TriMeOBQMOA is half of TriMeOBAPTQ (N,N,N′,N′-tetrakis(5,6,7-trimethoxy-2-quinolylmethyl)-1,2-bis(2-aminophenoxy)ethane), which is a tetrakisquinoline derivative of the well-known calcium chelator BAPTA (1,2-bis(2-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid). The fluorescent Cd2+ selectivity of TriMeOBAPTQ (IZn/ICd = 5.3% in the presence of 3 equiv of metal ions in MeOH–HEPES buffer (9:1)) comes from the formation of fluorescent dinuclear cadmium (M2L) and nonfluorescent OH-bridged dizinc ((μ-OH)M2L) complexes. TriMeOBQMOA also exhibits excellent Cd2+ specificity in fluorescence enhancement (IZn/ICd = 2.3% in the presence of 5 equiv of metal ions in DMF–HEPES buffer (1:1, HEPES 50 mM, KCl 0.1 M, pH = 7.5)) via substantial formation of a highly fluorescent bis(μ-chloro)dinuclear cadmium complex ([Cd2(μ-Cl)2L2]2+), which is in equilibrium with the mononuclear Cd2+ complex ([CdLCl]+), and extremely poor stability of the TriMeOBQMOA-Zn2+ complex. The all-nitrogen derivatives of BQMOA and BAPTQ, namely, N,N-BQDMPHEN (N,N-bis(2-quinolylmethyl)-N′,N′-dimethyl-1,2-phenylenediamine) and BPDTQ (N,N,N′,N′-tetrakis(2-quinolylmethyl)-2,2′-(N,N′-dimethylethylenediamino)dianiline), respectively, and their methoxy-substituted derivatives were also prepared, and the fluorescent metal ion sensing properties are discussed