Fluorescence sensing based on cation-induced conformational switching: copper-selective modulation of the photoinduced intramolecular charge transfer of a donor–acceptor biphenyl fluorophore

Abstract The fluorescence emission energy of donor–acceptor substituted biphenyls is highly sensitive towards conformational changes of the interannular twist angle. By integrating 4-dimethylamino-4′-cyano-biphenyl into the ligand backbone of a thioether-rich metal receptor we designed a fluorescence sensor that exhibits high selectivity towards copper. Upon metal binding the ligand undergoes a significant conformational change, which induces a strong hypsochromic shift of the photoinduced charge-transfer emission. Steady-state absorption and fluorescence spectroscopy revealed a high affinity towards Cu(I) with a well-defined 1:1 metal–ligand complex stoichiometry. The nature of the conformational changes upon Cu(I) coordination were analyzed in detail by 1 H NMR and 2D NOESY experiments. The spectroscopic data provide a coherent picture, which is consistent with a Boltzmann ground-state distribution of several rotamers that are locked into a more flattened geometry upon coordination of Cu(I).