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We report here the synthesis, characterization, and crystal structures of three perfluoropropylated dibenzo[ a , c ]phenazine constitutional isomers, in which the only difference among them was the positions of the perfluoropropyl substituents. The crystal structures of these perfluropropylated dibenzo[ a , c ]phenazine isomers indicated that the stereo-electronic effect of the perfluoropropyl group on the dibenzo[ a , c ]phenazine molecule plays a crucial role in determining the crystal-packing motif in the solid state. Our results from both X-ray crystallography and computational approaches revealed that the positions of the perfluoropropyl groups on the dibenzo[ a , c ]phenazine ring significantly affected the electrostatic potential distribution along the aromatic ring surface, resulting in drastic changes in the molecular packing in the solid state, from herringbone to lamellar crystal packing, among these three constitutional isomers. Simple topological consideration of the molecular packing in the solid state was coincidently cooperative with the changes in the electrostatic potential distributions, where localized partial positive and partial negative charges perhaps dominated the intermolecular interactions between the aromatic rings. Together, the perfluoropropylation on the dibenzo[ a , c ]phenazine ring provided us with a fortunate scenario, wherein the molecular topological structure and electrostatic potential worked together to facilitate the formation of the desired lamellar π–π stacked crystal packing. Meanwhile, electrochemistry, UV-visible absorption and emission spectra, and the computational chemistry results pointed out that there were only minor to moderate changes in the electronic properties of the molecules upon changing the position of the perfluoroalkylation on the dibenzo[ a , c ]phenazine core. While controlling the solid-state structure of aromatics by design still has a long way to go, we hope that our work will ignite a spark that can potentially spread into the field of the design of organic solid-state materials. 

In a simple, one-step reaction, we have synthesized a pyridoxal-based chemosensor by reacting tris(hydroxymethyl)aminomethane (TRIS) together with pyridoxal hydrochloride to yield a Schiff-base ligand that is highly selective for the detection of Zn( ii ) ion. Both the ligand and the Zn( ii ) complex have been characterized by 1 H & 13 C NMR, ESI-MS, CHN analyses, and X-ray crystallography. The optical properties of the synthesized ligand were investigated in an aqueous buffer solution and found to be highly selective and sensitive toward Zn( ii ) ion through a fluorescence turn-on response. The competition studies reveal the response for zinc ion is unaffected by all alkali and alkaline earth metals; and suppressed by Cu( ii ) ion. The ligand itself shows a weak fluorescence intensity (quantum yield, Φ = 0.04), and the addition of zinc ion enhanced the fluorescence intensity 12-fold (quantum yield, Φ = 0.48). The detection limit for zinc ion was 2.77 × 10 −8 M, which is significantly lower than the WHO's guideline (76.5 μM). Addition of EDTA to a solution containing the ligand–Zn( ii ) complex quenched the fluorescence, indicating the reversibility of Zn( ii ) binding. Stoichiometric studies indicated the formation of a 2 : 1 L 2 Zn complex with a binding constant of 1.2 × 10 9 M −2 (±25%). The crystal structure of the zinc complex shows the same hydrated L 2 Zn complex, with Zn( ii ) ion binding with an octahedral coordination geometry. We also synthesized the copper( ii ) complex of the ligand, and the crystal structure showed the formation of a 1 : 1 adduct, revealing 1-dimensional polymeric networks with octahedral coordinated Cu( ii ). The ligand was employed as a sensor to detect zinc ion in HEK293 cell lines derived from human embryonic kidney cells grown in tissue culture which showed strong luminescence in the presence of Zn( ii ). We believe that the outstanding turn-on response, sensitivity, selectivity, lower detection limit, and reversibility toward zinc ion will find further application in chemical and biological science.