Sensitive and selective PET-based diimidazole luminophore for Zn(II) ions: a structure-activity correlation.
3-(3-Ethoxymethyl-1H-imidazol-2-yl)-3-(1-ethoxymethyl-1H-imidazol-2-yl)-3H-benzo[de]isochromen-1-one, 4, is a novel photoinduced electron transfer (PET) chemosensor that becomes fluorescent upon binding metal ions and shows a strong preference toward Zn(II) ions. The new bisimidazol PET sensor and its zinc complex were prepared and characterized in terms of their crystal structures, absorption and emission spectra, and orbital energy diagrams. Free 4 is a weakly luminescent species. On the basis of detailed DFT calculations, we suggest that the poor luminescence yield of free 4 originates from its orbital structure in which two pi-orbitals of the two imidazole rings, HOMO and HOMO-1, are situated between two pi-orbitals of the isochromene-one system, HOMO-2 and LUMO. The absorption and emission processes occur between the two pi-orbitals of the isochromene-one system, HOMO-2 and LUMO, and the two pi-imidazole orbitals serve as quenchers for the excited state of the molecule through nonradiative processes. Upon binding Zn(II) ions, 4 becomes a highly luminescent species having a luminescence maximum peaking at 375 nm (lambda(ex) = 329 nm). The significant 900-fold enhancement in luminescence upon binding of the Zn(II) ions is attributed to the stabilization of the pi-orbitals of the imidazole rings upon their engagement in new bonds with the zinc ion. The affinity of 4 to zinc ions in acetonitrile is found to be very high, Ka > 3 x 10(6) M(-1), while with other metals ions, the association constants are considerably weaker.
Salman
Husein
H
Department of Chemistry and Solid State Institute, Israel Institute of Technology, Technion City, 32000 Haifa, Israel.
Tal
Shay
S
Chuvilov
Yulia
Y
Solovey
Olga
O
Abraham
Yael
Y
Kapon
Moshe
M
Suwinska
Kinga
K
Eichen
Yoav
Y
D001578:Benzopyrans / Q000138:chemical synthesis / Q000737:chemistry*; D002413:Cations, Divalent / Q000737:chemistry; D005456:Fluorescent Dyes / Q000737:chemistry*; D007093:Imidazoles / Q000138:chemical synthesis / Q000737:chemistry*; D049449:Luminescence; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012680:Sensitivity and Specificity; D013056:Spectrophotometry, Ultraviolet; D013329:Structure-Activity Relationship; D014961:X-Ray Diffraction; D015032:Zinc / Q000737:chemistry*
D001578:Benzopyrans; D002413:Cations, Divalent; D005456:Fluorescent Dyes; D007093:Imidazoles; D009942:Organometallic Compounds; D015032:Zinc