Effects of Intra- and Intermolecular Hydrogen Bonding on O-H Bond Photodissociation Pathways of a Catechol Derivative

The catechol functional motif is thought to play both a structural and photochemical role in the ubiquitous natural pigment, eumelanin. Intramolecular and intermolecular hydrogen bonding interactions lead to a variety of geometries involving the two O-H groups in catechol, but its photophysical behavior in these situations has not been comprehensively characterized. Toward this end, we monitor the UV-induced O-H bond photodissociation reaction in an exemplar catechol derivative, 4-tert-butylcatechol, possessing different intramolecular and intermolecular hydrogen bonding geometries using femtosecond transient absorption spectroscopy measurements in the UV-visible and mid-infrared regions following 265 nm photoexcitation. Three different hydrogen bonding arrangements are obtained by tuning solution complexation equilibria of the catechol with the hydrogen bond acceptor, diethyl ether (Et2O), and are verified computationally. We find that intermolecular hydrogen bonding to the free O-H group in catechol increases its first excited singlet state (SI) lifetime by 2 orders of magnitude (i.e., similar to 16 to 1410 ps), and that O-H bond dissociation is prevented because Et2O is a poor hydrogen atom acceptor. Complexation of both O-H groups with multiple Et2O molecules further elongates the S, lifetime to 1670 ps due to shifting of the solution equilibria that describe complex formation. Weakening of the characteristic, intramolecular hydrogen bond of the catechol derivative by intermolecular hydrogen bonding to one or more Et2O molecules does not enhance the rate of O-H bond dissociation.