Electronic Consequences of Nonplanar Core Conformations in Electron-Deficient Porphyrins: The Structure and Spectroscopic Properties of [5,10,15,20-Tetrakis(heptafluoropropyl)porphinato]cobalt(II)

Electrochemical study of the dication of porphyrins with carboxylic acids: Shift of the absorption bands compared to that of the redox potentials

“…The out-of-plane deformations of porphyrins and their influences on the electronic and NMR spectroscopy of the aromatic macrocycle have been of interest for chemists for more than two decades [1][2][3][4][5][6]. Chemical properties such as the basicity of two internal pyrrolenine nitrogen atoms, oxidation potentials of porphyrins and their metal complexes and binding affinity of the metal center to axial ligands are known to be modified by the out-of-plane deformations of the porphyrin core [3,7,8].…”

“…Accordingly, the dibasic properties of porphyrins may be utilized to induce different nonplanar distortions of the macrocycle, causing the shifts of the absorption bands in the UV-vis spectra and the chemicals shift of different protons in the NMR spectra. The HOMO/LUMO gap of porphyrins has been shown to be affected by the out-of-plane deformations of the macrocycle, leading to the shift of the Soret and Q bands [1][2][3][4][14][15][16][17]. The formation of donor-acceptor complexes between porphyrins and different acceptors is accompanied with the shift of electron density from the pyrrolenine nitrogens to the acceptor molecules and a decrease in the dihedral angles between the meso-aryl substituents and the porphyrin mean plane [2,14,17] which may also lead to the change of the energy level of the frontier orbitals of the porphyrins and the HOMO/LUMO gap.…”

“…The HOMO/LUMO gap of porphyrins has been shown to be affected by the out-of-plane deformations of the macrocycle, leading to the shift of the Soret and Q bands [1][2][3][4][14][15][16][17]. The formation of donor-acceptor complexes between porphyrins and different acceptors is accompanied with the shift of electron density from the pyrrolenine nitrogens to the acceptor molecules and a decrease in the dihedral angles between the meso-aryl substituents and the porphyrin mean plane [2,14,17] which may also lead to the change of the energy level of the frontier orbitals of the porphyrins and the HOMO/LUMO gap. Electrochemical properties of porphyrins and metalloporphyrins were found to be influenced by the electronic effects of substituents at the periphery of the porphyrin ring and nonplanar distortion of the macrocycle [3,[18][19][20].…”

Electrospray ionization (ESI) tandem mass spectrometric analysis of meso-tetrakis(heptafluoropropyl)porphyrin

“…Much less investigated are the corresponding meso-tetrakis-alkylporphyrins and mesoperfluoroalkylporphyrins [2][3][4][5]. In particular, the mesoperfluoroalkylporphyrins have proved useful in, for example, the design of synthetic monooxygenase mimicks [6].…”

Fluorinated Five‐Membered Nitrogen‐Containing Heterocycles

“…3.42). 79 There have been several reports of the synthesis of b-fluorinated porphyrins by construction of the macrocyclic ring using fluorinated pyrrole precursors. For (Fig.…”