44 / 2023-08-14 00:54:00

Hydrolysis of phosphorus (V) octaphenylporphyrazine: an unusual 3-membered product

Phosphorus (V) complexes,Macroheterocycles,Hydrolysis

New Technologies in Phosphorus Chemistry > 3) Organophosphorus coordination chemistry

Macroheterocyclic phosphorus (V) complexes attract the researchers by a wide range of their unique properties. P^V phthalocyanines have a record singlet oxygen quantum yields [1] and are capable to absorb light in NIR region [2]. P^V corrolazines are photosensitizers with fluorescent response on media conditions [3]. This complexes are also able to DNA photocleavage [4]. P^V porphyrins have been used as the basis for molecular turnstiles building, which can be used as switchers or sensors on some cationic effectors [5]

Recently a process of reversible nucleophilic addition to a P^V phthalocyanine core at one of α-pyrrolic carbon atoms was reported [6]. Such kind of nucleophilic addition breaking aromaticity of macrocycle and leads to strong distortion of phthalocyanine geometry.

In this work, we have found a process of hydrolysis of phosphorus (V) octaphenylporphyrazine. Such kind of the process leads to formation of stable tripyrrolic phosphorus complex.

Macroheterocyclic phosphorus (V) complexes attract the researchers by a wide range of their unique properties. P^V phthalocyanines have a record singlet oxygen quantum yields [1] and are capable to absorb light in NIR region [2]. P^V corrolazines are photosensitizers with fluorescent response on media conditions [3]. This complexes are also able to DNA photocleavage [4]. P^V porphyrins have been used as the basis for molecular turnstiles building, which can be used as switchers or sensors on some cationic effectors [5]

Recently a process of reversible nucleophilic addition to a P^V phthalocyanine core at one of α-pyrrolic carbon atoms was reported [6]. Such kind of nucleophilic addition breaking aromaticity of macrocycle and leads to strong distortion of phthalocyanine geometry.

In this work, we have found a process of hydrolysis of phosphorus (V) octaphenylporphyrazine. Such kind of the process leads to formation of stable tripyrrolic phosphorus complex.

Fig. 1. Scheme (left) and spectral changes (right) upon hydrolysis of P^V octaphenylporphyrazine in pyridine



The structure of this product was confirmed using MALDI-TOF mass-spectrometry, IR, ¹H and ³¹P NMR spectroscopy. Geometry of investigated tripyrrolic phosphorus complex was investigated using quantum chemical calculations. The process of hydrolysis was investigated in organic solvents, such as pyridine, acetone, DMSO and CH₂Cl₂. The thermodynamics of this process is also described using quantum chemical calculations.

This complex have unusual fluorescent properties. In CH₂Cl₂ the maxima of fluorescence are observed at 490 and 528 nm with excitation at 350 nm, but this compound have also a broad absorption peak at 425-675nm with maximum at 530nm. Excitation in this broad peak does not induce fluorescence



This work was supported by Russian Foundation of basic research (grant № 20-53-26004)



Keywords：Phosphorus (V) complexes; Macroheterocycles; Hydrolysis



Reference

[1] Safonova E.A; Kolomeychuk F.M.; Gvozdev D.A.; et al. Molecules, 2023, 28(3), 1094.

[2] Furuyama T.; Kobayashi N. Phys. Chem. Chem. Phys. 2017, 19, 15596-15612.

[3] Lazovskiy D.A.; Skvortsov I.A.; Novakova V.; Stuzhin P.A. Dalton Trans. 2022, 51, 5687-5698.

[4] Huang L.; Zhong C.; Zhang F.; Tung Ch.-H. Bioorganic Med. Chem. Lett. 2008, 18(6), 2152-2155.

[5] Meshkov I.N.; Bulach V.; Gorbunova Yu.G.; et al. Inorg. Chem. 2016, 55(20), 10774–10782.

[6] Kolomeychuk F.M.; Safonova E.A; Polovkova M.A.; et al. J. Am. Chem. Soc. 2021, 143(35), 14053–14058