Analysis of the spectral properties and structural differences of two turn-on ratiometric fluorescent receptors for Zn2+ and Cd2+ ions, derivatives of pyrrolo[2,3-b]quinoxaline (2), and earlier published 3 (Ostrowska et al. CrystEngComm 2015, 17, 498-502) was performed. Both ligands are E/Z push pull olefins interconverting at room temperature, with barriers to rotation about enamine double bonds, from E to Z isomers of 19.3 +/- 0.1 and 16.9 +/- 0.3 kcal/mol and from Z to E of 16.9 +/- 0.3 and 15.7 +/- 0.2 kcal/mol, respectively. Diastereoisomers (E)-2 and (Z)-2 were isolated and characterized by X-ray structural analysis. The formation of complexes by (E/Z)-2 with acetates and acetylacetonates of Zn2+ and Cd2+ was monitored by UV-vis, fluorescence, and H-1 NMR titrations in acetonitrile, respectively. X-ray structural analysis for isolated [(E)-2](2)Zn in relation to earlier published (E)-3-ZnOAc revealed the formation of a six-coordinated zinc ion with six- and four-membered bis-chelate rings by (E)-2. The chelate effect increases the ligand affinity for Zn2+ (log beta(12) = 12.45) and causes the elongation of nitrogen metal bonds. Extension of the coordination cavity size allows coordination of a cadmium ion. The introduction of a flexible ethylene linker between the fluorophore and ionophore pyridyl groups in 3 significantly affects the selectivity of zinc-ion recognition. The distorted tetrahedral geometry of (E)-3-ZnOAc with a four-coordinated zinc ion appears to be the most preferred because of the short donor zinc distance with a 1:1 binding mode. The formation of the small coordination cavity size with six-membered bis-chelate rings provides an effective overlap of zinc and donor orbitals, precluding the coordination of a cadmium ion in the same manner as zinc.