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Tuning light-driven oxidation of styrene inside water-soluble nanocages.

ABSTRACT: Selective functionalization of innate sp² C-H bonds under ambient conditions is a grand synthetic challenge in organic chemistry. Here we combine host-guest charge transfer-based photoredox chemistry with supramolecular nano-confinement to achieve selective carbonylation of styrene by tuning the dioxygen concentration. We observe exclusive photocatalytic formation of benzaldehyde under excess O₂ (>1 atm) while Markovnikov addition of water produced acetophenone in deoxygenated condition upon photoexcitation of confined styrene molecules inside a water-soluble cationic nanocage. Further by careful tuning of the nanocage size, electronics, and guest preorganization, we demonstrate rate enhancement of benzaldehyde formation and a complete switchover to the anti-Markovnikov product, 2-phenylethan-1-ol, in the absence of O₂. Raman spectroscopy, 2D ¹H-¹H NMR correlation experiments, and transient absorption spectroscopy establish that the site-selective control on the confined photoredox chemistry originates from an optimal preorganization of styrene molecules inside the cavity. We envision that the demonstrated host-guest charge transfer photoredox paradigm in combination with green atom-transfer reagents will enable a broad range of sp² carbon-site functionalization.

SUBMITTER: Ghosal S

PROVIDER: S-EPMC10902312 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature

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Tuning light-driven oxidation of styrene inside water-soluble nanocages.

Ghosal Souvik S Das Ankita A Roy Debojyoti D Dasgupta Jyotishman J

Nature communications 20240228 1

Selective functionalization of innate sp<sup>2</sup> C-H bonds under ambient conditions is a grand synthetic challenge in organic chemistry. Here we combine host-guest charge transfer-based photoredox chemistry with supramolecular nano-confinement to achieve selective carbonylation of styrene by tuning the dioxygen concentration. We observe exclusive photocatalytic formation of benzaldehyde under excess O<sub>2</sub> (>1 atm) while Markovnikov addition of water produced acetophenone in deoxygena ...[more]

PMID: 38418497

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Project description:The elucidation of the ideal coordination environment of a catalytic site has been at the heart of catalytic applications. Herein, we show that the water oxidation activities of catalytic cobalt sites in a Prussian blue (PB) structure could be tuned systematically by decorating its coordination sphere with a combination of cyanide and bidentate pyridyl groups.  K0.1[Co(bpy)]2.9[Fe(CN)6]2 ([Cobpy-Fe]), K0.2[Co(phen)]2.8[Fe(CN)6]2 ([Cophen-Fe]), {[Co(bpy)2]3[Fe(CN)6]2}[Fe(CN)6]1/3 ([Cobpy2-Fe]), and {[Co(phen)2]3[Fe(CN)6]2}[Fe(CN)6]1/3 Cl0.11 ([Cophen2-Fe]) were prepared by introducing bidentate pyridyl groups (phen: 1,10-phenanthroline, bpy: 2,2'-bipyridine) to the common synthetic protocol of Co-Fe Prussian blue analogues. Characterization studies indicate that [Cobpy2-Fe] and [Cophen2-Fe] adopt a pentanuclear molecular structure, while [Cobpy-Fe] and [Cophen-Fe] could be described as cyanide-based coordination polymers with lower-dimensionality and less crystalline nature compared to the regular Co-Fe Prussian blue analogue (PBA), K0.1Co2.9[Fe(CN)6]2 ([Co-Fe]). Photocatalytic studies reveal that the activities of [Cobpy-Fe] and [Cophen-Fe] are significantly enhanced compared to those of [Co-Fe], while molecular [Cobpy2-Fe] and [Cophen2-Fe] are inactive toward water oxidation. [Cobpy-Fe] and [Cophen-Fe] exhibit upper-bound turnover frequencies (TOFs) of 1.3 and 0.7 s-1, respectively, which are ∼50 times higher than that of [Co-Fe] (1.8 × 10-2 s-1). The complete inactivity of [Cobpy2-Fe] and [Cophen2-Fe] confirms the critical role of aqua coordination to the catalytic cobalt sites for oxygen evolution reaction (OER). Computational studies show that bidentate pyridyl groups enhance the susceptibility of the rate-determining Co(IV)-oxo species to the nucleophilic water attack during the critical O-O bond formation. This study opens a new route toward increasing the intrinsic water oxidation activity of the catalytic sites in PB coordination polymers.

Dataset Information

Tuning light-driven oxidation of styrene inside water-soluble nanocages.

Publications

Tuning light-driven oxidation of styrene inside water-soluble nanocages.

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