Metal–Organic Cyclohelicates as Optical Receptors for Glutathione: Syntheses, Structures, and Host–Guest Behaviors

Abstract

Two trinuclear zinc-based cyclohelicates, Zn-PDB (PDB = [5-(dibenzylamino)-N1',N3'-bis(pyridin-2-ylmethylene)isophthalohydrazide]) and Zn-PMB (PMB = [5-(bodipy-oxy)-N1',N3'-bis(pyridin-2-ylmethylene)isophthalohydrazide]) containing dibenzylamino and BODIPY groups, respectively, were generated by incorporating two amide-containing tridentate chelators into meta-positions of a substituted phenyl ring. Single-crystal structure analysis and related spectroscopic characterizations demonstrated the formation of macrocyclic helicals both in the solid state and in solution. The host-guest behavior of the cyclohelical hosts towards γ-glutamyl-cysteinyl-glycine (GSH) and its component amino acids was investigated by spectroscopic titrations. UV/Vis absorption titration and NMR titrations of Zn-PDB and Zn-PMB upon addition of the above-mentioned guests suggested that the Glu residue of GSH was positioned within the cavity. The COO(-) groups interacted with metal ions through static interactions. The Cys moiety of GSH interacted with the amide groups sited in host molecules through hydrogen-bonding interactions to produce measurable spectral changes. Fluorescent titrations of Zn-PMB upon the addition of GSH and ESI-MS investigations of the titration solutions confirmed the host-guest interaction modes and revealed the possible 1:1 complexation stoichiometry. These results showed that the recognition of a substrate within the cavity of functionalized metal-organic cage-like receptors could be a useful method to produce supramolecular sensors for biomolecules.