Synthesis And Properties Study Of Tb(â…¢) Complex Probes Base On The Antenna Effect Of Cyclic Nitrogen Ligands

Org anic ligands enable the rare earth ions that has a special4f electron shell structure emit excellent luminescent by the "Antenna Effect". By adjusting the structure of the complex ligands can achieve excellent luminescent properties, we can also choose different functional ligands to achieve the recognition of a particular substance.Thus functional rare earth luminescent complexes has been widely used in coordination chemistry, supramolecular chemistry, materials chemistry and so on, it has become a hot and challenging topic now. The macrocyclic nitrogen ligands has better selectivity to rare earth ions, and the structure of complexes is stable and has better luminescent properties than the relative open-loop system.This article is based on the principle of "Antenna Effect", starting from pyridine-2,6-dicarboxylic acid designed and synthesized seven macrocyclic nitrogen compounds, we choice two of the seven teeth ligands hmpydioneN6Am and acpydioneN6Am react with TbCl3synthesized complexes Tbl and Tb2, and the structures of the ligands and complexes were characterized. The UV spectroscopy and fluorescence spectroscopy confirmed that the ligands and terbium ions can produce good "Antenna effect", and can be applied in a wide range of pH.Terbium ion is nine-coordinated metal, synthesized seven teeth ligands are not satisfied with the coordination number of terbium ions, so anions can be detected base on the theory. Test results show that in many anions (PO43-, HPO42-, H2PO4-, CO32-, HCO3-, S2O32-,SO4-, HSO4-, SO32-, HSO3-, AcO-, S2-,CN-,SCN-, I-, Br, Cl-,F-, NO2-, NO3-) the probe Tb series only have good selective response for NO2-. By the fluorescence titration data we calculate the linear equv.uations of probe Tbl, Tb2detect NO2-are I1=-400.32X-1601.94, I2=-360.80X-1366.81, the lowest detection limits were1.03×10-7mol/L,6.8×10-8mol/L. To verify the practical application of this method, we use two probes to detect the content of commercial pickle’s NO2-. Experimental results show that the probe Tb series can detect the NO2-of the actual food samples qualitative and quantitative.PolypHospHates are good polydentate ligands, it’s easy to coordinate with metal ions. In order to explore the impact of multi-tooth ligand groups to luminescent probes, we test the response of two probes to different polypHospHates(ATP, ADP, AMP, PO43-, HPO42-, H2PO4-). The results show that probe Tbl and Tb2have preferably selective response to ATP that containing three polydentate groups. The tridentate of ATP is easier coordinate with Tb3+to interference the "Antenna Effect", which changes the fluorescence emission. ATP interact with probe Tbl in1:1, due to the structure of probe Tb2, the luminescent of probe Tb2was significant quenching after added lequv. ATP. The lowest detection limit of probe Tbl and Tb2reaches4.25×10-8mol/L,4.27×10-8mol/L.In short, the probe Tb series not only can detect trace NO2-both in the environment and food, but also can test ATP in vivo. Experimental results show that it has broad practical value.