Theoretical and experimental mechanistic insights of CO release by water soluble Re(I) photoCORMs

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta Pub Date : 2025-05-31 DOI:10.1016/j.ica.2025.122788

Vitor C. Weiss , Giliandro Farias , Suélen M. Amorim , André L. Amorim , Daniele C. Durigon , Fernando R. Xavier , Regina de F.P.M. Moreira , Adailton J. Bortoluzzi , Rosely A. Peralta

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引用次数: 0

Abstract

The use of photoCORMs to release carbon monoxide in a specific biological target has been widely studied because their therapeutic properties. This work presents the synthesis and photochemical and mechanistic insight of the CO photorelease of three water-soluble Re(I) photoCORMs: [Re(aaz)(CO)₃]Cl (1), [Re(Me₂aaz)(CO)₃]Cl (2), and [Re(tacn)(CO)₃]Cl (3) (aaz = 6-amino-6-methylperhydro-1,4-diazepine; Me₂aaz = 6-amino-1,4,6-trimethyl-1,4-diazacycloheptane; and tacn = 1,4,7-triazacyclononane). All compounds presented photo-triggered carbon monoxide release when exposed to UV light (λ₂₅₄ = 254 ± 10 nm), affording bis and monocarbonyl intermediates identified via spectroscopic, electrochemical, and mass techniques. The quantum yields and rates of CO release were determined where its release mechanism probably involves a three-step mechanistic pathway. Despite recent studies, the mechanism of CO release associated with Re(I) photoCORMs and spin-orbit coupling has not been explored in-depth, and it could be a critical factor in developing new and more efficient photoCORMs.

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水溶性Re(I)光corms释放CO的理论和实验机理研究

由于其治疗特性，利用光微粒在特定生物靶标中释放一氧化碳已被广泛研究。本文介绍了三种水溶性Re(I)光合成物：[Re(aaz)(CO)3]Cl (1), [Re(Me2aaz)(CO)3]Cl(2)和[Re(tacn)(CO)3]Cl (3) (aaz = 6-氨基-6-甲基过氢-1,4-二氮卓；Me2aaz = 6-氨基-1,4,6-三甲基-1,4-二氮杂环庚烷；tacn = 1,4,7-三氮杂环壬烷)。所有化合物暴露在紫外光（λ254 = 254±10 nm）下均表现出光触发一氧化碳释放，提供通过光谱、电化学和质量技术鉴定的双羰基和单羰基中间体。测定了CO的量子产率和释放速率，其中CO的释放机制可能涉及三步机制途径。尽管近年来研究较多，但CO释放与Re(I)光自旋轨道耦合相关的机制尚未深入探讨，这可能是开发新型高效光自旋轨道耦合的关键因素。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.