How Electronic Excitation Can be Used to Inhibit Some Mechanisms Associated to Substituent Effects

Despite the fact that transferability and chemistry go hand in hand, transferability studies in electronically excited states (EESs) are normally omitted, although these states are becoming extremely important in modern processes and applications. In this work, it is shown that this kind of studies can be used to understand how substituent effects can be modified in EESs. Thus, for example, the analysis of the carbonyl oxygen transferability in different HCO-R molecules allowed us to find that the nO→πCO* excitation can be used to break the π conjugation associated to the resonance substituent effect. Moreover, as a direct consequence, the oxygen transferability is enhanced in the first electronically excited state.