Water-soluble sulfonated phosphorus(v) corrolazines and porphyrazines: the effect of macrocycle contraction and pyrazine ring fusion on spectral, acid-base and photophysical properties

0550871 - ÚFCH JH 2023 RIV GB eng J - Journal Article
Ivanova, S. S. - Salnikov, D. S. - Knorr, G. - Ledovich, O. - Sliznev, V. - Kubát, Pavel - Nováková, V. - Stuzhin, P. A.
Water-soluble sulfonated phosphorus(v) corrolazines and porphyrazines: the effect of macrocycle contraction and pyrazine ring fusion on spectral, acid-base and photophysical properties.
Dalton Transactions. Roč. 51, č. 4 (2022), s. 1364-1377. ISSN 1477-9226. E-ISSN 1477-9234
Institutional support: RVO:61388955
Keywords : singlet oxygen * photodynamic therapy * 1st corrolazine * metal-complexes * phthalocyanines * state * subphthalocyanines * tetraazaporphyrin * electrochemistry * porphyrinoids
OECD category: Physical chemistry
Impact factor: 4, year: 2022
Method of publishing: Limited access

Novel water-soluble dihydroxophosphorus(v) complexes of sulphophenyl substituted porphyrazine (6), corrolazine (7) and its pyrazine fused derivative (8) were prepared and their spectral, acid-base and photophysical properties in aqueous solutions were studied. Due to the presence of eight SO3H groups, the compounds were fully monomeric (7 and 8) or only slightly aggregated (6) in water. Spectrophotometric titration revealed that the two stage deprotonation of axially bonded hydroxy groups can be achieved for porphyrazine 6 (pK(a1) = 5.62, pK(a2) = 9.13) and pyrazine fused corrolazine 8 (pK(a1) = 6.5, pK(a2) = 11.7), while only the first dissociation stage could be observed for corrolazine 7 (pK(a1) = 9.94). The fluorescence emission of the corrolazines 7, 8 and especially porphyrazine 6 was low in water (Phi(F) = 0.086, 0.18, and 0.014, respectively) and completely quenched under basic conditions due to photoinduced electron transfer. In comparison with porphyrazine 6, the contraction of the macrocycle in the corrolazines 7 and 8 induced significant improvement of singlet oxygen production in water reaching values of Phi(Delta) = 0.56 and 0.43, respectively, which makes the corrolazines promising photosensitizers for photodynamic therapy. The observed evolution of the electronic absorption spectra and fluorescence quenching observed in a basic medium was explained using the model DFT calculations (cc-pvtz basis set) performed for the dihydroxophosphorus(v) complexes of unsubstituted porphyrazine and corrolazine and their mono- and doubly deprotonated forms.
Permanent Link: http://hdl.handle.net/11104/0326178