Tuning Fluorescence and Singlet Oxygen Quantum Yields of Subporphyrazines by Axial Functionalization.

Autor: Ben Ahmed S; Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain., Pérez de Bustos G; Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain., Pina J; University of Coimbra, CQC-IMS, Department of Chemistry, Rua Larga, 3004-535, Coimbra, Portugal., Torres T; Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain.; Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain.; IMDEA-Nanociencia, c/Faraday 9, Cantoblanco, 28049, Madrid, Spain., Rodríguez-Morgade MS; Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain.; Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain.
Jazyk: angličtina
Zdroj: ChemPlusChem [Chempluschem] 2024 May; Vol. 89 (5), pp. e202300779. Date of Electronic Publication: 2024 Feb 06.
DOI: 10.1002/cplu.202300779
Abstrakt: The axial functionalization of Subporphyrazines (SubPzs) with unreported alkoxy groups, carboxy and carboperoxy rests, as well as sulfanyl, aryl and amino groups, forming B-O, B-S, B-C, and B-N bonds, respectively, has been investigated. The studied oxygen nucleophiles include aromatic and sterically demanding aliphatic alcohols, along with carboxylic acids and peracids. In general, direct substitution of the chloro-SubPz by oxygen nucleophiles of diverse nature proceeds smoothly, with yields of the isolated alkoxy and carboxy-substituted SubPzs ranging from 49 to 100 %. Conversely, direct substitution with sulphur, carbon and nitrogen nucleophiles do not afford the corresponding substituted SubPzs. In these cases, a stepwise procedure involving an axial triflate-SubPz intermediate was employed, affording only the phenyl-SubPz in 8 % yield. The major compound under these conditions was the unreported SubPz μ-oxo dimer, presumably arising from substitution of the triflate-SubPz by the in situ generated hydroxy-SubPz. This result indicates a quite low reactivity of the TfO-SubPz intermediate with carbon, sulphur and nitrogen nucleophiles. All SubPzs prepared in this work exhibited fluorescence at 510-515 nm with quantum yields ranging from 0.1 to 0.24. Additionally, all SubPzs generated singlet oxygen, with Φ Δ values ranging from 0.15 to 0.57, which show no apparent correlation with the axial substituents.
(© 2024 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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