A Perylene Bisimide Cyclophane as a "Turn-On" and "Turn-Off" Fluorescence Probe

A rigid, covalently linked perylene-3,4: 9,10-tetra-carboxylic acid bisimide (PBI) cyclophane was synthesized by imidization of a bay-substituted perylene bisanhydride with p-xylylenediamine. The interchromophoric distance of approximately 6.5 angstrom establishes an ideal rigid cavity for the encapsulation of large aromatic compounds such as perylene and anthracene with binding constants up to 4.6 x 10(4) M-1 (in CHCl3). For electron-poor guest molecules, the complexation process is accompanied by a significantly increased fluorescence, whereas the emission intensity is dramatically quenched by more electron-rich guests because of the formation of charge-transfer complexes. Furthermore, the influence of the PBI core twist on the binding constant results in a remarkable selectivity towards more flexible aromatic guest molecules.