N-H-Type Excited-State Proton Transfer in Compounds Possessing a Seven-Membered-Ring Intramolecular Hydrogen Bond.

A series of compounds containing 5-(2-aminobenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one (o-ABDI) as the core chromophore with a seven-membered-ring N-H-type intramolecular hydrogen bond have been synthesized and characterized. The acidity of the N-H proton and thus the hydrogen-bond strength can be fine-tuned by replacing one of the amino hydrogen atoms by a substituent R, the acidity increasing with increasing electron-withdrawing strength of R, that is, in the order H<COCH3 <COPh<Tosyl<COCF3 . The tosyl and trifluoroacetyl derivatives undergo ultrafast, irreversible excited-state intramolecular proton transfer (ESIPT) that results in proton-transfer emission solely in the red region. Reversible ESIPT, and hence dual emission, involving the normal and proton-transfer tautomers was resolved for the acetyl- and benzyl-substituted counterparts. For o-ABDI, which has the weakest acidity, ESIPT is prohibited due to its highly endergonic reaction. The results clearly demonstrate the harnessing of ESIPT by modifying the proton acidity and hydrogen-bonding strength in a seven-membered-ring intramolecular hydrogen-bonding system. For all the compounds studied, the emission quantum yields are weak (ca. 10(-3) ) in dichloromethane, but strong in the solid form, ranging from 3.2 to 47.4 %.