Rational design of fluorescent chemosensor for Pd²⁺ based on the formation of cyclopalladated complex

According to the assumption that the formation of C-Pd bond becomes a cyclopalladated complex (CPC), we designed and synthesized two C-N-N pincer ligands of BODIPY appended 2,2'-bipyridine derivatives (BP and BPB). It has been confirmed that the C-Pd bond does exist and plays a crucial role in "on-off" fluorescence behavior. Based on it, a coordination-induced fluorescence quenching sensor for Pd²⁺ was constructed. The results indicated that BP possessed high sensitivity and specificity for Pd²⁺ in solution. The limit of detection (LOD) of BP is determined to be 0.97 nM within a linear range between 1.0 and 50.0 nM, meanwhile, the platinum-group ions demonstrate no interference. The bio-imaging application of BP was investigated and it exhibited a promising vitro test for fluorescent imaging of Pd²⁺ ions in MCF-7 cells. Meanwhile, BPB coated sensor label for Pd²⁺ was set up. The visible color variation was displayed under UV light with increasing concentrations of Pd²⁺. Briefly speaking, fluorescence probes of BP and BPB offer new approaches for Pd²⁺ detection in a lab and on-site test, as well as the vivo imaging. Then, with the aid of (TD)DFT calculation, the internal reason for the optical difference between the two ligands was disclosed. This concept of CPC containing a Pd-C covalent bond provides a promising perspective of coordination fluorescence sensors.