Synthesis and characterization of fluorophores for the detection of lanthanides and actinides

A series of fluorophores based in the boron dipyrromethene (BODIPY) family were synthesized and characterized. These fluorophores have the capacity of being introduced to a carbamoyl methyl phosphine oxide (CMPO) lanthanide/actinide extractant. These blue, green and red emission fluorophores show high thermal/moisture stability and high fluorescence efficiencies. The fluorescence intensity seems to be dependent on the restricted rotation about the C(8)-C bond in 8-Ph-BODIPY. By taking advantage of this feature, a hydroxyl- containing BODIPY with high fluorescence intensity was synthesized to be incorporated to a CMPO carboxylic acid via esterification. Unfortunately, we did not observe an optical response upon the coordination of the single CMPO-fluorophore ligand to various lanthanides.;The generality of the reaction between primary amines and secondary amines and 8-MeS-BODIPY is also discussed along with the optical properties of the new amino-BODIPY fluorophores. The most important feature observed was the significant dependence of their fluorescence intensity with respect to solvent polarity variation.;Following the same nucleophilic substitution type of reaction, we explored the generality of nucleophilic substitution of 8-MeS-BODIPY by several alkyl- and aryl- thiols under mild conditions. We also observed that polysubstitution is possible by changing the solvent. The optical features and x-ray crystal structures are herein described.;Lastly, a mass spectrometric - collision-induced dissociation (MS-CID) study of lanthanides and various CMPOs is described. It was found that a tridentate CMPO has the capacity to form bis(ligand), nitrate-free complexes with several lanthanides.