Bibliographic Details
| Title: |
Phosphorus(V) tetrapyrazinocorrolazines bearing axial aryloxy groups as pH-sensitive fluorophores and photosensitizers. |
| Authors: |
Lazovskiy DA; Research Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology, RF-153000 Ivanovo, Russia. stuzhin@isuct.ru., Skvortsov IA; Research Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology, RF-153000 Ivanovo, Russia. stuzhin@isuct.ru., Novakova V; Faculty of Pharmacy in Hradec Kralove, Charles University, 500 05 Hradec Kralove, Czech Republic., Stuzhin PA; Research Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology, RF-153000 Ivanovo, Russia. stuzhin@isuct.ru. |
| Source: |
Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2022 Apr 05; Vol. 51 (14), pp. 5687-5698. Date of Electronic Publication: 2022 Apr 05. |
| Publication Type: |
Journal Article |
| Language: |
English |
| Journal Info: |
Publisher: Royal Society of Chemistry Country of Publication: England NLM ID: 101176026 Publication Model: Electronic Cited Medium: Internet ISSN: 1477-9234 (Electronic) Linking ISSN: 14779226 NLM ISO Abbreviation: Dalton Trans Subsets: MEDLINE; PubMed not MEDLINE |
| Imprint Name(s): |
Original Publication: Cambridge, UK : Royal Society of Chemistry, c2003- |
| 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. |
| Entry Date(s): |
Date Created: 20220324 Latest Revision: 20220405 |
| Update Code: |
20260130 |
| DOI: |
10.1039/d2dt00307d |
| PMID: |
35322831 |
| Database: |
MEDLINE |