Solution or solid – it doesn't matter: visible light-induced CO release reactivity of zinc flavonolato complexes

Anderson, Stacey N.; Larson, Michael T.; Berreau, Lisa M.

doi:10.1039/c6dt01709f

Cited by 19 publications

(18 citation statements)

References 84 publications

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“…Enzymatically triggered processes or a solvent-mediated ligand exchange usually result in a poor spatial and temporal control over the release profile. On the contrary, prevalent CO-releasing metal–carbonyl complexes − retain a metal backbone upon CO release, which can lead to unwanted reactions with adjacent cells …”

Section: Introductionmentioning

confidence: 99%

Mechanisms of Orthogonal Photodecarbonylation Reactions of 3-Hydroxyflavone-Based Acid–Base Forms

et al. 2020

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Carbon monoxide is a naturally occurring gasotransmitter combining inherent toxicity with a remarkable therapeutic potential and arduous administration. Photoactivatable carbon monoxide-releasing molecules (photoCORMs) are chemical agents that allow for precise spatial and temporal control over the CO release. In this work, we present a comprehensive mechanistic study of the photochemical CO release from 3-hydroxy-2-phenyl-4H-chromen-4-one, a π-extended 3-hydroxyflavone photoCORM, in methanol using steady-state and transient absorption spectroscopies and quantum chemical calculations. The multiplicity of the productive excited states and the role of oxygen (O2) in the CO production are emphasized, revealing a photoreaction dichotomy of the 3-hydroxyflavone acid and base forms. The utilization of three major orthogonal mechanistic pathways, all of which lead to the CO release, can fuel future endeavors to improve the CO release efficacy of 3-hydroxyflavone-based derivatives and refine their potential medical applications as photoCORMs.

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Section: Introductionmentioning

confidence: 99%

Mechanisms of Orthogonal Photodecarbonylation Reactions of 3-Hydroxyflavone-Based Acid–Base Forms

et al. 2020

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“…An interesting novel feature of a class of photoCORMs bearing flavonato derivatives was demonstrated by Berreau and coworkers [76]. They reported two types of Zn(II) flavonolato complexes that exhibit red-shift energy absorbance and enhanced CO release compared to the free corresponding flavonols.…”

Section: Organic Photocormsmentioning

confidence: 93%

Visible Light-Activated PhotoCORMs

Kottelat

Zobi

2017

Inorganics

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Despite its well-known toxicity, carbon monoxide (CO) is now recognized as a potential therapeutic agent. Its inherent toxicity, however, has limited clinical applications because uncontrolled inhalation of the gas leads to severe systemic derangements in higher organisms. In order to obviate life-threatening effects and administer the gas by bypassing the respiratory system, CO releasing molecules (CORMs) have emerged in the last decades as a plausible alternative to deliver controlled quantities of CO in cellular systems and tissues. As stable, solid-storage forms of CO, CORMs can be used to deliver the gas following activation by a stimulus. Light-activated CORMs, known as photoCORMs, are one such example. This class of molecules is particularly attractive because, for possible applications of CORMs, temporal and spatial control of CO delivery is highly desirable. However, systems triggered by visible light are rare. Most currently known photoCORMs are activated with UV light, but red light or even infrared photo-activation is required to ensure that structures deeper inside the body can be reached while minimizing photo-damage to healthy tissue. Thus, one of the most challenging chemical goals in the preparation of new photoCORMs is the reduction of radiation energy required for their activation, together with strategies to modulate the solubility, stability and nontoxicity of the organic or organometallic scaffolds. In this contribution, we review the latest advances in visible light-activated photoCORMs, and the first promising studies on near-infrared light activation of the same.

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“…Zinc complexation of 1 – 4 provided the first examples of divalent metal flavonolato complexes ( 6 – 13 , Scheme 20) that exhibit O 2 -dependent, quantitative visible light-induced solid-state CO release [119]. Similar to the solution reactivity of 1 – 3 , these zinc complexes undergo reaction either in solution or in the solid state to produce Zn(II) O -benzoylsalicylate complexes (Scheme 20) and one equivalent of CO per flavonolato ligand.…”

Section: Visible Light-induced Co Release From Extended 3-hydroxyfmentioning

confidence: 99%

“…The quantum yields for the reactions of 6 – 9 are enhanced relative to the free flavonols (Table 2). Limited solubility of the Zn(II) bis-flavonolato complexes 10 – 13 in common organic solvents enabled the use of 10 as a visible light driven in situ CO release compound for palladium-catalyzed carbonylation [119].…”

Section: Visible Light-induced Co Release From Extended 3-hydroxyfmentioning

confidence: 99%

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3-Hydroxyflavones and 3-Hydroxy-4-oxoquinolines as Carbon Monoxide-Releasing Molecules

Soboleva

Berreau

2019

Molecules

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Carbon monoxide-releasing molecules (CORMs) that enable the delivery of controlled amounts of CO are of strong current interest for applications in biological systems. In this review, we examine the various conditions under which CO is released from 3-hydroxyflavones and 3-hydroxy-4-oxoquinolines to advance the understanding of how these molecules, or derivatives thereof, may be developed as CORMs. Enzymatic pathways from quercetin dioxygenases and 3-hydroxy-4-oxoquinoline dioxygenases leading to CO release are examined, along with model systems for these enzymes. Base-catalyzed and non-redox-metal promoted CO release, as well as UV and visible light-driven CO release from 3-hydroxyflavones and 3-hydroxy-4-oxoquinolines, are summarized. The visible light-induced CO release reactivity of recently developed extended 3-hydroxyflavones and a 3-hydroxybenzo[g]quinolone, and their uses as intracellular CORMs, are discussed. Overall, this review provides insight into the chemical factors that affect the thermal and photochemical dioxygenase-type CO release reactions of these heterocyclic compounds.

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Solution or solid – it doesn't matter: visible light-induced CO release reactivity of zinc flavonolato complexes

Cited by 19 publications

References 84 publications

Mechanisms of Orthogonal Photodecarbonylation Reactions of 3-Hydroxyflavone-Based Acid–Base Forms

Mechanisms of Orthogonal Photodecarbonylation Reactions of 3-Hydroxyflavone-Based Acid–Base Forms

Visible Light-Activated PhotoCORMs

3-Hydroxyflavones and 3-Hydroxy-4-oxoquinolines as Carbon Monoxide-Releasing Molecules

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