Intramolecular resonance-assisted hydrogen bonds (RAHBs) are stronger than conventional hydrogen bonds (HBs) thanks to the extra stabilization connected with the partial delocalization of the pi-electrons within the HB motif containing conjugated formally single and double bonds. When these conjugated bonds are part of an aromatic ring, there is an interplay between resonance-assisted hydrogen bonding and the aromaticity of the ring. The main aim of the present work is to analyze the changes in RAHB strength by substitution in the aromatic ring. For this purpose, we use density functional theory methods to study all possible mono- and di-substitutions in the four free positions of the aromatic ring in o-hydroxybenzaldehyde. As substituents, we consider three pi-electron donating groups (EDG: NH2, OH, and F) and three pi-electron withdrawing groups (EWG: NO2, NO, and CN). We show that it is possible to tune the HB bond distance in the RAHB by locating different substituents in given positions of the aromatic ring. Indeed, certain combinations of EDG and EWD result in a reduction or increase of the HB distance by up to 0.05 Å. Results found can be explained by considering the existence of a resonance effect of the π-electrons within the HB motif

We are grateful for financial support from the Spanish MINECO (CTQ2017-85341-P), the Catalan DIUE (2014SGR931, XRQTC, and ICREA Academia 2014 Award to M.S.), and the FEDER fund (UNGI10-4E-801)