Correlation among Hydrogen Bond, Excited-State Intramolecular Proton-Transfer Kinetics and Thermodynamics for −OH Type Proton-Donor Molecules

Abstract

A series of new molecules bearing alkyl-substitutes on the parent molecule 1-hydroxy-11H-benzo[b]fluoren-11-one (HBF) has been designed and synthesized, which possesses an intramolecular hydrogen bond (H-bond) between −OH proton donor and carbonyl proton acceptor. All studied molecules present an equilibrium type of excited-state intramolecular proton transfer (ESIPT) at 298 K. The alkyl-substitutions at various positions subtly alter the intramolecular H-bond strength, which then fine-tune the excited-state equilibrium and hence thermodynamics between normal and tautomer species. These, in combination with finite rates of ESIPT resolved by femtosecond fluorescence upconversion techniques, lead to the establishment of an empirical relationship among H-bond strengths, ESIPT kinetics, and thermodynamics for HBF series of molecules, in which the stronger H-bond is, the faster and more exergonic ESIPT is. The intensity ratio for normal versus proton-transfer tautomer emission can be systematically tuned, demonstrating the harness of −OH type ESIPT reaction via facile alkyl-substituent perturbation.