(1,6)Pyrenophanes containing crown ether moieties as fluorescence sensors for metal and ammonium ions. Formation of sandwich, dumbbell, and pseudorotaxane complexes

(1,6)Pyrenophanes 1 and 2 in which 1,6-positions of pyrene are bridged with respective tri- and tetra-ethylene glycol chains were synthesized. Addition of Ba(ClO4)(2) to a 10(-5) M CH2Cl2 : CH3CN = 1 : 1 solution of 1 reduced the intramolecular excimer emission with a maximum at 480 nm and increased the monomer emission around 370-400 nm. In contrast, addition of Ba(ClO4)(2) to the solution of 2 shifted the intramolecular excimer emission to shorter wavelengths. Addition of n-Bu2NH2+PF6- to the solutions of 1 and 2 both decreased the intramolecular excimer emission and increased the monomer emission. Based on the results of these fluorescence changes, Job's plots, and NMR titration, it is concluded that 1 forms a 1 : 1 sandwich-type complex with Ba2+, 2 forms a 1 : 2 dumbbell-type complex with Ba2+, and both 1 and 2 form pseudorotaxanes with n-Bu2NH2+. It was also found that when the pyrenophanes 1 and 2 were mixed with tetracyanoethylene (TCNE) in CH2Cl2, charge-transfer (CT) complexes were formed, that exhibited absorption maxima at 740 and 744 nm, respectively.

Automated summary

Pyrenophanes 1 and 2 with bridged pyrene at 1,6-positions by tri- and tetra-ethylene glycol chains were synthesized. Addition of Ba(ClO4)(2) affected the fluorescence emission of 1 and 2 differently. n-Bu2NH2+PF6- also had an impact on the fluorescence emission of both compounds. Complexation of Ba2+ with 1 and 2, as well as the formation of pseudorotaxanes with n-Bu2NH2+ was confirmed. Moreover, charge-transfer complexes were formed when pyrenophanes 1 and 2 were mixed with TCNE in CH2Cl2.