Stabilization of Photocatalytically Active Uranyl Species in a Uranyl-Organic Framework for Heterogeneous Alkane Fluorination Driven by Visible Light.,Inorganic Chemistry

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Stabilization of Photocatalytically Active Uranyl Species in a Uranyl-Organic Framework for Heterogeneous Alkane Fluorination Driven by Visible Light.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-06-02 , DOI: 10.1021/acs.inorgchem.0c00850
Xuan Zhang ₁ , Peng Li ₁ , Matthew Krzyaniak _{1,

2} , Julia Knapp , Michael R Wasielewski ₁ , Omar K Farha ₁

Affiliation

When photoactivated, the uranyl ion is a powerful oxidant capable of abstracting hydrogen atoms from nonactivated C–H bonds. However, the highly reactive singly reduced [U^VO₂]⁺ intermediate is unstable with respect to disproportionation to the uranyl dication and insoluble tetravalent uranium phases, which limits the usage of uranyl ions as robust photocatalysts. Herein, we demonstrate that photoactivated uranyl ions can be stabilized by immobilizing and separating them spatially in a uranyl–organic framework heterogeneous catalyst, NU-1301. The visible-light-photoactivated uranyl ions in NU-1301 exhibited longer-lived U(V) and radicals than those in homogeneous counterparts, as evidenced by X-ray photoelectron spectroscopy and time-dependent electron paramagnetic resonance, leading to higher turnovers and enhanced stability for the fluorination of nonactivated alkanes.

中文翻译：

在可见光驱动的非均相烷烃氟化铀酰-有机构架中稳定光催化活性的铀酰。

当被光活化时，铀酰离子是一种强大的氧化剂，能够从未活化的C–H键中提取氢原子。但是，高反应性会单独还原[U ^V O ₂ ] ⁺中间体在关于铀酰指示剂和不溶性四价铀相的歧化方面是不稳定的，这限制了将铀酰离子用作坚固的光催化剂。在这里，我们证明光活化的铀酰离子可以通过在铀酰-有机骨架非均相催化剂NU-1301中固定和分离它们而稳定。X射线光电子能谱和随时间变化的电子顺磁共振表明，NU-1301中可见光激活的铀酰离子比同质对应物具有更长寿命的U（V）和自由基。非活化烷烃氟化的稳定性。

更新日期：2020-06-02

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