Phenol-containing bis(oxazolines): synthesis and fluorescence sensing of amines

Abstract

The fluorescence sensing of primary amines as their neutral forms has been studied with bis(oxazolinyl)phenols (Me-BOP, Ph-BOP), which are efficiently synthesized starting from mesitylene in six steps and in overall 12-22% yields. The BOP sensors showed fluorescence enhancement toward butylamine and several arylethylamines, whereas they showed fluorescence quenching toward secondary and branched amines. The opposite fluorescence behavior is explained by an increased conformational restriction at the excited state, at which a proton transfer complex between the host and guest forms that is stabilized in a tripodal hydrogen bonding mode. This is the first example in which fluorescence enhancement is observed in amine sensing with phenolic fluorophores. Enantiomeric alpha-chiral organoamines were also sensed with different fluorescent intensity changes by Ph-BOP, complementing the previous tris(oxazolines) that sense enantiomeric alpha-chiral organoammonium ions. (c) 2006 Elsevier Ltd. All rights reserved.