Solid-State Dynamic Behavior of the Boron–Nitrogen Bond Enables Mechanophotocatalysis of a [2 + 2]-Photocycloaddition

IF 8.5 Q1 CHEMISTRY, MULTIDISCIPLINARY

JACS Au Pub Date : 2026-09-28 Epub Date: 2026-08-21 DOI:10.1021/jacsau.6c00942

Alaric Shaw, Peter F. Gilbert, Ivan Bondarenko, Kokoro K. Holcomb, Paulina M. Sittinger, Jesus Daniel Loya, Simon J. Teat, Nicholas S. Settineri, Gonzalo Campillo-Alvarado

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Abstract

We report reversible B←N coordinate bond formation and cleavage in the organic solid state. The dynamic behavior was probed using the [2 + 2]-photodimerization of 4-(1-naphthylvinyl)pyridine (4-nvp) as a chemical reporter under concurrent mechanochemical vortex grinding and ultraviolet light-emitting diode (UV-LED) irradiation. Phenylboronic acid catechol ester (pbe) templates the regio- and stereoselective formation of 1,3-bis(4-pyridyl)-2,4-bis(1-naphthyl)cyclobutane (pncb), and the reaction proceeds efficiently even when pbe is used in substoichiometric amounts (50%, 30% and 5% mol). The catalytic turnover demonstrates that B←N bonds can break and reform dynamically under mechanical stress in the organic solid state, establishing B←N coordination as a design element for responsive molecular materials.

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硼氮键的固态动力学行为实现了[2 + 2]-光环加成的机械光催化

我们报道了有机固体中可逆的b←N坐标键的形成和裂解。以4-（1-萘基乙烯基）吡啶（4-nvp）的[2 + 2]-光二聚化反应作为化学报告剂，在机械化学涡流研磨和紫外发光二极管（UV-LED）同步照射下研究了其动力学行为。苯硼酸邻苯二酚酯（pbe）可为1,3-二（4-吡啶基）-2,4-二（1-萘基）环丁烷（pncb）的立体选择性生成提供模板，即使pbe在亚化学计量量（50%、30%和5%mol）下也能有效地进行反应。催化翻转表明，在有机固体状态下，B←N键可以在机械应力下动态断裂和重组，从而建立了B←N配位作为响应分子材料的设计元素。

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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