Effect of Moderate Hydrogen Bonding on Tautomer Formation via Excited-State Intermolecular Proton-Transfer Reactions in an Aromatic Urea Compound with a Steric Base.

Abstract

1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU), which forms weak hydrogen bonds despite the high basicity caused by its hindered structure, was used to investigate tautomer formation via excited-state intermolecular proton-transfer (ESPT) reactions. The kinetics of the ESPT reactions of anthracen-2-yl-3-phenylurea (2PUA) in the presence of DBU were compared to that observed for the acetate anion (Ac) using time-resolved fluorescence measurement. Based on the association constants in the ground state, the intermolecular hydrogen bond between 2PUA and DBU was less stable than the bond between 2PUA and Ac due to steric hindrance and the geometry of the hydrogen bond. In the fluorescence spectra, 2PUA-DBU displayed prominent tautomeric emission in chloroform (CHCl3), whereas 2PUA-Ac exhibited distinct tautomeric emissions in dimethyl sulfoxide (DMSO). Kinetic analysis revealed that the rate constant of the ESPT reaction of 2PUA-DBU remarkably decreased when the proton-accepting ability of the solvent increased whereas the reaction of 2PUA-Ac was linked to the solvent polarity rather than proton-accepting ability. These results indicated that moderate hydrogen bonds due to steric hindrance were influenced by the type of solvent present, particularly if the solvents exhibited proton-accepting capabilities like DMSO. This, in turn, affected the rate constant of tautomer formation.