N-Aromatic Complexation in Tetraphenyl Porphyrin Iron (III)-Pyridine: Evidence of Spin-Flip via Gas-Phase Electronic...

There is growing interest in the electronic properties of metalloporphyrins especially in relation to their interactions with other molecular species in their local environment. Here, UV-VIS laser photodissociation spectroscopy in vacuo has been applied to an iron-centred metalloporphyrin (FeTPP⁺) and its N-aromatic adduct with pyridine (py) to determine the electronic effect of complexation. Both the metalloporphyrin (FeTPP⁺) and pyridine adduct (FeTPP⁺⋅py) absorb strongly across the spectral region studied (652-302 nm: 1.91-4.10 eV). Notably, a large blue shift was observed for the dominant Soret band (41 nm) upon complexation (0.47±0.02 eV), indicative of strong pyridine binding. Significant differences in the profiles (i. e. number and position of bands) of the electronic spectra are evident comparing FeTPP⁺ and FeTPP⁺⋅py. Time-dependent density functional theory calculations were used to assign the spectra, revealing that the Fe^III spin-state flips from S=3/2 to S=5/2 upon complexation with pyridine. For FeTPP⁺, all bright spectral transitions are found to be π-π* in character, with electron density variously distributed across the porphyrin and/or its phenyl substituents. Similar electronic excitations are observed for FeTPP⁺⋅py, with an additional bright transition which involves charge transfer from the porphyrin to the pyridine moiety.