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

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11160%2F22%3A10450588" target="_blank" >RIV/00216208:11160/22:10450588 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=-OdG4LlLk3" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=-OdG4LlLk3</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d2dt00307d" target="_blank" >10.1039/d2dt00307d</a>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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, phi(F) similar to 0.16-0.31) and is efficient to generate singlet oxygen (phi(Delta) = 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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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, phi(F) similar to 0.16-0.31) and is efficient to generate singlet oxygen (phi(Delta) = 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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

30104 - Pharmacology and pharmacy

Projekt

<a href="/cs/project/GC21-14919J" target="_blank" >GC21-14919J: Porfyrazinoidy s nekovovými centrálními atomy jako nové perspektivní fotosenzitizéry a fluorescenční senzory</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2022

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

51

Číslo periodika v rámci svazku

14

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

12

Strana od-do

5687-5698

Kód UT WoS článku

000772507700001

EID výsledku v databázi Scopus

2-s2.0-85127624935