Photoinduced electron transfer in non-covalent free-base octaethylporphyrin and 2-nitrofluorene donor-acceptor system: A combined experimental and quantum chemical study

A photobasic D–A fluorophore with a high intramolecular charge-transfer as a model strategy for designing organic proton-coupled electron-transfer modulators: an analysis based on steady-state fluorescence, isotopic effect and theoretical study

“…In the search for an organic modulator of PCET processes, herein we introduce the inclusion of a weak basic moiety into the D-A chain of the fluorophore and this together with the occurrence of an ICT along this D-A chain upon excitation could be two essential points for constructing a convenient organic photobasic PCET modulator (Scheme 1C). Organic fluorophores based on donor-acceptor (D-A) systems have been widely employed as photoinduced electron transfer (PET) modulators, [36][37][38][39][40][41][42][43] but further investigations are needed to extend their application for identifying PCET mechanisms.…”

“…In the search for an organic modulator of PCET processes, herein we introduce the inclusion of a weak basic moiety into the D–A chain of the fluorophore and this together with the occurrence of an ICT along this D–A chain upon excitation could be two essential points for constructing a convenient organic photobasic PCET modulator (Scheme 1C). Organic fluorophores based on donor–acceptor (D–A) systems have been widely employed as photoinduced electron transfer (PET) modulators, 36–43 but further investigations are needed to extend their application for identifying PCET mechanisms. The ICT process usually occurs in donor (D)–acceptor (A) chemical systems through a charge transfer from the D-group to the A-group upon excitation, which generates an anomalous excited (charge transfer) CT state from the normal locally excited (LE) state.…”

Amphiphilic Porphyrin Aggregates: A DFT Investigation

“…Therefore, the same geometry optimization in the vacuum has been performed using WB97XD functional and 6-31G(d) basis set (Figures 9-11), considering counterpoise correction. Long-range interactions, as well as the empirical dispersion term of van der Waals, are included in such functionals, and both constitute significant contributions in the energy calculation of π-π stacked dimers and cationic species [39,45,46]. The optimized H-type aggregate converged to a partially differently organized structure, where the two porphyrin cores were slightly staggered to each other ( Figure 6).…”