Synthesis and Anion Sensing of Water-Soluble Metallomacrocycles

The self-assembly of (TMEDA)Pd(NO(3))(2) or (TMEDA)Pt(NO(3))(2) (where TMEDA = N(1),N(1),N(2),N(2)-tetramethylethane-1,2-diamine) and anthracene- or ferrocene-based diimidazole ligands (L(1-3)) in aqueous solution affords a series of positively charged [M(2)L(2)](4+) dimetallomacrocycles. Their structures were characterized by (1)H NMR and electrospray ionization mass spectrometry and in the cases of {[(TMEDA)Pd](2)L(2)(1)}(NO(3))(4) (1), {[(TMEDA)Pd](2)L(2)(1)}(PF(6))(4) (1a), and {[(TMEDA)Pd](2)L(2)(3)}(NO(3))(4) (4) by single-crystal X-ray diffraction analysis. Interestingly, the NMR spectra of 1 and la revealed that the difference of their structures, as confirmed by X-ray diffraction analysis, was that a NO(3)(-) of 1 was encapsulated inside the cavity of the basket-shaped metallomacrocycle by C-H center dot center dot center dot O hydrogen bonds, while PF(6)(-) of 1a was bound outside by C-H center dot center dot center dot F hydrogen bonds. The fluorescence titration experiment exhibited the formation of 1:1 host guest complexation for anthracene-based positively charged [M(2)L(2)](4+)-type metallomacrocycles with NO(3)(-). The interactions between metallomacrocycles and various anions were investigated via fluorescence titration and cyclic voltammetry studies, respectively.