To avoid the use of hydrofluoric acid, a series of fluorinated trivalent and tetravalent metal-containing phthalocyanines (MPcs) were synthesized using a straightforward one-step halide substitution process using cesium fluoride (CsF) as the fluoride source and by reflux in N,N-dimethylformamide for less than an hour. The resulting fluoro MPcs were characterized and compared to the parent chloro MPcs. In some cases, very little change in properties was observed between the fluoro MPcs and the chloro MPcs. In other cases, such as fluoro aluminum phthalocyanine, a blue shift in the absorbance characteristics and an increase in oxidation and reduction potential of as much as 0.22 V was observed compared to the chloro derivative. Thermo gravimetric analysis was performed on all halo-MPcs, indicating that the choice of halo substitution on the axial position can have an effect on the decomposition or sublimation temperature of the final compound. After initial establishment and characterization of the fluoro MPcs, the halide substitution reaction of difluoro silicon phthalocyanine (F2-SiPc) was further explored by scaling the reaction up to a gram scale as well as considering tetrabutylammonium fluoride (TBAF) as an additional safe fluoride source. The scaled-up reactions producing F2-SiPc using CsF and TBAF as fluoride exchange sources were successfully reproducible, resulting in reaction yields of 100 and 73%, respectively. Both processes led to pure final products but results indicate that CsF, as the fluoride exchange reagent, appears to be the superior reaction process as it has a much higher yield.

The efficiency of a fluorescence sensing device based on metal-enhanced fluorescence (MEF) is dependent on the optimization of interaction between the fluorophore and the metal nanoparticle (NP). Herewith, ultrasensitive and selective turn-on sensing of Au3+ is achieved by using a suitable combination of fluorophore and metal NP system through sequential MEF effect. Dansyl hydrazide-tagged Ag NPs in the polyacryloyl hydrazide cavity are utilized to sense the picomolar concentration of Au3+ in aqueous media. We demonstrated that the selective Au3+ sensing is due to the selective deposition of Au on the Ag NP surface over the 16 other metal ions studied. The sensitivity is assigned to the strong overlapping of the emission band of the fluorophore with the surface plasmon band of the Au and improvement of fluorescence signal through successive MEF by Ag and Au colloids. The sensing is associated with a fivefold increase in fluorescence intensity and appearance of violet color of the solution. These luminescent Ag-Au bimetallic NPs may be utilized to trace cancer cells in biological systems and for cell imaging applications.