Synthesis and Functional Properties of Fluorinated Phosphonate‐Substituted Porphyrins: Excellent Photosensitizers and Robust Precursors for Photoactive Langmuir–Schaefer Films

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 ‐tetrakis[4‐(diethoxyphosphoryl)‐2,3,5,6‐tetrafluorophenyl]porphyrin (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.