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

New Journal of Chemistry Pub Date: 2022-12-09 DOI: 10.1039/D2NJ04790J

Abstract

(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.

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