ABSTRACT Fluorinated porphyrins have attracted considerable attention in PDT, sensing and catalysis. Guided by demands for functional porphyrins with tunable electronic properties, high photostability, and controlled supramolecular organization, we report a synthetic approach to meso ‐tetrakis4‐(diethoxyphosphoryl)‐2,3,5,6‐tetrafluorophenylporphyrin (H 2 TF 4 PPP), which combines the advantages of diethyl phosphonate and fluorine substituents within a highly symmetrical porphyrin molecule. X‐ray diffraction analysis of H 2 TF 4 PPP reveals that diethyl phosphonates govern the crystal packing, while the macrocycles avoid π–π stacking. Zn(II) and Pd(II) complexes with H 2 TF 4 PPP were prepared in high yields. In contrast, insertion of In(III) ions exhibiting strong Lewis acidity was accompanied by partial hydrolysis of phosphonate groups. H 2 TF 4 PPP and its Zn(II) and Pd(II) complexes efficiently generate singlet oxygen displaying a good solubility in various organic solvents. The noble‐metal‐free porphyrin H 2 TF 4 PPP surpasses Pd(II) complex of non‐fluorinated analogue (PdTPPP) in photocatalytic performance, enabling sustainable oxidation of sulfides to sulfoxides with oxygen. H 2 TF 4 PPP forms a stable Langmuir monolayer which can be transferred onto solid substrates, yielding dense single‐layer films containing fiber‐shaped nanoparticles. The films thus obtained are emissive and their photostability surpasses that of H 2 TPPP films. Water‐soluble porphyrins H 2 TF 4 PPP‐A and PdTF 4 PPP‐A with phosphonic acid groups were also prepared and briefly investigated.
Kechiche et al. (Fri,) studied this question.