Chelate Ring Size Effect as a Factor of Selective Fluorescent Recognition of Zn(2+) Ions by Pyrrolo[2,3-b]quinoxaline with a Substituted 2-Pyridyl Group Receptor.
Analysis of the spectral properties and structural differences of two turn-on ratiometric fluorescent receptors for Zn(2+) and Cd(2+) 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 Zn(2+) and Cd(2+) was monitored by UV-vis, fluorescence, and (1)H NMR titrations in acetonitrile, respectively. X-ray structural analysis for isolated [(E)-2]2Zn 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 Zn(2+) (log β12 = 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.
Department of Organic Chemistry, Jagiellonian University , R. Ingardena 3, PL-30060 Kraków, Poland.
Katarzyna
K
Ostrowska
Department of Organic Chemistry, Jagiellonian University , R. Ingardena 3, PL-30060 Kraków, Poland.
Bogdan
B
Musielak
Department of Organic Chemistry, Jagiellonian University , R. Ingardena 3, PL-30060 Kraków, Poland.
Edward
E
Szneler
Department of Organic Chemistry, Jagiellonian University , R. Ingardena 3, PL-30060 Kraków, Poland.
Łukasz
Ł
Dudek
Department of Organic Chemistry, Jagiellonian University , R. Ingardena 3, PL-30060 Kraków, Poland.
Marlena
M
Gryl
Department of Organic Chemistry, Jagiellonian University , R. Ingardena 3, PL-30060 Kraków, Poland.
Katarzyna
K
Stadnicka
D002614:Chelating Agents / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005453:Fluorescence; D007477:Ions / Q000032:analysis; D008958:Models, Molecular; D015394:Molecular Structure; D010316:Particle Size; D011725:Pyridines / Q000138:chemical synthesis / Q000737:chemistry*; D011810:Quinoxalines / Q000737:chemistry; D015032:Zinc / Q000032:analysis*
D002614:Chelating Agents; D007477:Ions; D011725:Pyridines; D011810:Quinoxalines; C000608165:pyrrolo(2,3-b)quinoxaline; D015032:Zinc