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Synthesis and molecular structure of perhalogenated rhenium-oxo corroles.

ABSTRACT: As part of our efforts to develop rhenium-oxo corroles as photosensitizers for oxygen sensing and photodynamic therapy, we investigated the potential β-perhalogenation of five ReO meso-tris(para-X-phenyl)corroles, Re[TpXPC](O) (X = CF₃, H, F, CH₃, and OCH₃), with elemental chlorine and bromine. With Cl₂, β-octachlorinated products Re[Cl₈TpXPC](O) were rapidly obtained for X = CF₃, H, and CH₃, but X = OCH₃ resulted in overchlorination on the meso-aryl groups. Full β-octabromination proved slower relative to Cu and Ir corroles, but the desired Re[Br₈TpXPC](O) products were finally obtained for X = H and F after a week at room temperature. For X = CH₃ and OCH₃, these conditions led to undecabrominated products Re[Br₁₁TpXPC](O). Compared to the β-unsubstituted starting materials, the β-octahalogenated products were found to exhibit sharp ¹H NMR signals at room temperature, indicating that the aryl groups are locked in place by the β-halogens, and substantially redshifted Soret and Q bands. Single-crystal X-ray structures of Re[Cl₈TpCF₃PC](O), Re[Cl₈TpCH₃PC](O), and Re[Br₈TpFPC](O) revealed mild saddling for one Cl₈ structure and the Br₈ structure. These structural variations, however, appear too insignificant to explain the slowness of the β-octabromination protocols, which seems best attributed to the deactivating influence of the high-valent Re center.

SUBMITTER: Alemayehu AB

PROVIDER: S-EPMC7665048 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Synthesis and molecular structure of perhalogenated rhenium-oxo corroles.

Alemayehu Abraham B AB Einrem Rune F RF McCormick-McPherson Laura J LJ Settineri Nicholas S NS Ghosh Abhik A

Scientific reports 20201112 1

As part of our efforts to develop rhenium-oxo corroles as photosensitizers for oxygen sensing and photodynamic therapy, we investigated the potential β-perhalogenation of five ReO meso-tris(para-X-phenyl)corroles, Re[TpXPC](O) (X = CF3, H, F, CH3, and OCH3), with elemental chlorine and bromine. With Cl2, β-octachlorinated products Re[Cl8TpXPC](O) were rapidly obtained for X = CF3, H, and CH3, but X = OCH3 res ...[more]

PMID: 33184456

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Project description:The increase in the antibiotic resistance of bacteria is a serious threat to public health. Photodynamic inactivation (PDI) of micro-organisms is a reliable antimicrobial therapy to treat a broad spectrum of complex infections. The development of new photosensitizers with suitable properties is a key factor to consider in the optimization of this therapy. In this sense, four corroles were designed to study how the number of cationic centers can influence the efficacy of antibacterial photodynamic treatments. First, 5,10,15-Tris(pentafluorophenyl)corrole (Co) and 5,15-bis(pentafluorophenyl)-10-(4-(trifluoromethyl)phenyl)corrole (Co-CF3) were synthesized, and then derivatized by nucleophilic aromatic substitution with 2-dimethylaminoethanol and 2-(dimethylamino)ethylamine, obtaining corroles Co-3NMe2 and Co-CF3-2NMe2, respectively. The straightforward synthetic strategy gave rise to macrocycles with different numbers of tertiary amines that can acquire positive charges in an aqueous medium by protonation at physiological pH. Spectroscopic and photodynamic studies demonstrated that their properties as chromophores and photosensitizers were unaffected, regardless of the substituent groups on the periphery. All tetrapyrrolic macrocycles were able to produce reactive oxygen species (ROS) by both photodynamic mechanisms. Uptake experiments, the level of ROS produced in vitro, and PDI treatments mediated by these compounds were assessed against clinical strains: methicillin-resistant Staphylococcus aureus and Klebsiella pneumoniae. In vitro experiments indicated that the peripheral substitution significantly affected the uptake of the photosensitizers by microbes and, consequently, the photoinactivation performance. Co-3NMe2 was the most effective in killing both Gram-positive and Gram-negative bacteria (inactivation > 99.99%). This work lays the foundations for the development of new corrole derivatives having pH-activable cationic groups and with plausible applications as effective broad-spectrum antimicrobial photosensitizers.

Dataset Information

Synthesis and molecular structure of perhalogenated rhenium-oxo corroles.

Publications

Synthesis and molecular structure of perhalogenated rhenium-oxo corroles.

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