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Phosphorus(V) tetrapyrazinocorrolazines bearing axial aryloxy groups as pH-sensitive fluorophores and photosensitizers.

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Title: Phosphorus(V) tetrapyrazinocorrolazines bearing axial aryloxy groups as pH-sensitive fluorophores and photosensitizers.
Authors: Lazovskiy, Dmitriy A.1 (AUTHOR), Skvortsov, Ivan A.1 (AUTHOR), Novakova, Veronika2 (AUTHOR), Stuzhin, Pavel A.1 (AUTHOR) stuzhin@isuct.ru
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 4/14/2022, Vol. 51 Issue 14, p5687-5698. 12p.
Subjects: Reactive oxygen species, Photoinduced electron transfer, Fluorophores, Molecular orbitals, Excited states, Phosphorus, Dimethyl sulfoxide
Abstract: Phosphorus(V) complexes of octaphenyltetrapyrazinocorrolazine bearing two aryloxy groups in the axial position, [TPyzCAP(OAr)2] (2a–c, Ar = phenyl (2a), 4-dimethylaminophenyl (2b), and 4-hydroxyphenyl (2c)), were prepared using a one-pot procedure by consecutive treatment of the dihydroxidophosphorus(V) derivative, [TPyzCAP(OH)2] (1), with SOCl2 and then with the corresponding phenol ArOH. Complex 2a containing axial PhO groups is fluorescent in all studied solvents (toluene, CH2Cl2, THF, and DMSO, ΦF ∼ 0.16–0.31) and is efficient to generate singlet oxygen (ΦΔ = 0.55 (THF), 0.68 (toluene)). The introduction of NMe2 and OH groups in the para-position of the axial ArO ligands strongly affects the fluorescence parameters and photosensitizing properties due to the appearance of the solvent-sensitive and pH-switchable effects of photoinduced electron transfer (PET). The PET effect of NMe2 groups completely quenches the excited state of 2b in all solvents, but it is switched-OFF upon their protonation, and in the presence of acid traces, the fluorescence of 2b becomes bright and singlet oxygen generation is strongly enhanced. The PET effect of the OH group is increased upon its deprotonation and in the presence of base 2c as well as 1 becomes non-fluorescent. Specific solvation in THF and DMSO increases the ionic character of the OH bonds, and the fluorescence and photosensitizing properties of 1 and 2c are strongly decreased in these solvents. According to the results of DFT calculations performed using the B3LYP functional with the cc-pVDZ basis set and cyclic voltammetric studies, the molecular orbitals localized on aryloxy ligands are destabilized upon the introduction of OH and especially NMe2 groups and their close position to the HOMO of corrolazine macrocycle (above HOMO in 2b and between HOMO and HOMO−1 in 2c) leads to the appearance of the PET effect. [ABSTRACT FROM AUTHOR]
Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Phosphorus(V) tetrapyrazinocorrolazines bearing axial aryloxy groups as pH-sensitive fluorophores and photosensitizers.
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  Data: <searchLink fieldCode="AR" term="%22Lazovskiy%2C+Dmitriy+A%2E%22">Lazovskiy, Dmitriy A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Skvortsov%2C+Ivan+A%2E%22">Skvortsov, Ivan A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Novakova%2C+Veronika%22">Novakova, Veronika</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Stuzhin%2C+Pavel+A%2E%22">Stuzhin, Pavel A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> stuzhin@isuct.ru</i>
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  Data: <searchLink fieldCode="DE" term="%22Reactive+oxygen+species%22">Reactive oxygen species</searchLink><br /><searchLink fieldCode="DE" term="%22Photoinduced+electron+transfer%22">Photoinduced electron transfer</searchLink><br /><searchLink fieldCode="DE" term="%22Fluorophores%22">Fluorophores</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+orbitals%22">Molecular orbitals</searchLink><br /><searchLink fieldCode="DE" term="%22Excited+states%22">Excited states</searchLink><br /><searchLink fieldCode="DE" term="%22Phosphorus%22">Phosphorus</searchLink><br /><searchLink fieldCode="DE" term="%22Dimethyl+sulfoxide%22">Dimethyl sulfoxide</searchLink>
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  Data: Phosphorus(V) complexes of octaphenyltetrapyrazinocorrolazine bearing two aryloxy groups in the axial position, [TPyzCAP(OAr)2] (2a–c, Ar = phenyl (2a), 4-dimethylaminophenyl (2b), and 4-hydroxyphenyl (2c)), were prepared using a one-pot procedure by consecutive treatment of the dihydroxidophosphorus(V) derivative, [TPyzCAP(OH)2] (1), with SOCl2 and then with the corresponding phenol ArOH. Complex 2a containing axial PhO groups is fluorescent in all studied solvents (toluene, CH2Cl2, THF, and DMSO, ΦF ∼ 0.16–0.31) and is efficient to generate singlet oxygen (ΦΔ = 0.55 (THF), 0.68 (toluene)). The introduction of NMe2 and OH groups in the para-position of the axial ArO ligands strongly affects the fluorescence parameters and photosensitizing properties due to the appearance of the solvent-sensitive and pH-switchable effects of photoinduced electron transfer (PET). The PET effect of NMe2 groups completely quenches the excited state of 2b in all solvents, but it is switched-OFF upon their protonation, and in the presence of acid traces, the fluorescence of 2b becomes bright and singlet oxygen generation is strongly enhanced. The PET effect of the OH group is increased upon its deprotonation and in the presence of base 2c as well as 1 becomes non-fluorescent. Specific solvation in THF and DMSO increases the ionic character of the OH bonds, and the fluorescence and photosensitizing properties of 1 and 2c are strongly decreased in these solvents. According to the results of DFT calculations performed using the B3LYP functional with the cc-pVDZ basis set and cyclic voltammetric studies, the molecular orbitals localized on aryloxy ligands are destabilized upon the introduction of OH and especially NMe2 groups and their close position to the HOMO of corrolazine macrocycle (above HOMO in 2b and between HOMO and HOMO−1 in 2c) leads to the appearance of the PET effect. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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      – Type: doi
        Value: 10.1039/d2dt00307d
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      – Code: eng
        Text: English
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        PageCount: 12
        StartPage: 5687
    Subjects:
      – SubjectFull: Reactive oxygen species
        Type: general
      – SubjectFull: Photoinduced electron transfer
        Type: general
      – SubjectFull: Fluorophores
        Type: general
      – SubjectFull: Molecular orbitals
        Type: general
      – SubjectFull: Excited states
        Type: general
      – SubjectFull: Phosphorus
        Type: general
      – SubjectFull: Dimethyl sulfoxide
        Type: general
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      – TitleFull: Phosphorus(V) tetrapyrazinocorrolazines bearing axial aryloxy groups as pH-sensitive fluorophores and photosensitizers.
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            NameFull: Lazovskiy, Dmitriy A.
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            NameFull: Skvortsov, Ivan A.
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            NameFull: Novakova, Veronika
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            NameFull: Stuzhin, Pavel A.
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            – D: 14
              M: 04
              Text: 4/14/2022
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              Y: 2022
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