Visible Light-Activatable Organoboron Complexes Featuring Salicylaldehyde Azine Ligands for Rapid Cationic Polymerization and Mechanism Studies.

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-07-04 DOI:10.1021/acs.inorgchem.5c00783

Yingzhu Sun, Lei Wang, Changjiang Yu, Zihao Wang, Jinsong Shao, Xinsheng Xu, Yaxiong Wei, Yangyang Xu, Lijuan Jiao, Erhong Hao

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引用次数: 0

Abstract

Rapid polymerization controlled by visible light holds great potential for advancing 3D printing technologies. However, a significant challenge limiting the implementation of visible-light-activated polymerizations is its low efficiency compared to UV light driven processes. To address this, we developed a series of visible-light-activatable organoboron (BOSHY) complexes featuring salicylaldehyde azine ligands for rapid cationic polymerization. These BOSHYs featuring different brominated BOSHY catalyze the polymerization of epoxides under 405 nm LED light in three-component systems with iodonium salt and amine, achieving a 78% epoxy conversion in just 52 s at low intensity irradiation of 50 mW cm^-2. Additionally, the mechanism of photopolymerization involves the formation of cations by EDB, which initiates the polymerization process. The triplet state lifetime (15.4-23.5 μs) indicates effective intersystem crossing, enabling efficient energy and electron transfer reactions. Experiments confirm nearly 100% electron transfer due to the extended triplet state lifetime. This study not only introduces novel BOSHY derivatives for cationic polymerization but also elucidates the reaction kinetics analysis of the photopolymerization, significantly expanding the use of visible light LEDs as an alternative to UV light in photopolymerization.

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以水杨醛-嗪为配体的可见光可活化有机硼配合物的快速阳离子聚合及其机理研究。

由可见光控制的快速聚合对于推进3D打印技术具有巨大的潜力。然而，与紫外光驱动的工艺相比，可见光激活聚合的效率较低，这是限制其实施的一个重大挑战。为了解决这个问题，我们开发了一系列以水杨醛嗪配体为特征的可见光可活化有机硼（BOSHY）配合物，用于快速阳离子聚合。这些具有不同溴化BOSHYs的BOSHYs在405 nm LED光下与碘盐和胺在三组分体系中催化环氧化合物聚合，在50 mW cm-2的低强度照射下，仅52 s就实现了78%的环氧化合物转化率。此外，光聚合的机理涉及EDB形成阳离子，从而引发聚合过程。三重态寿命（15.4 ~ 23.5 μs）表明了有效的系统间交叉反应，实现了高效的能量和电子转移反应。实验证实，由于延长了三重态寿命，电子转移率接近100%。本研究不仅介绍了用于阳离子聚合的新型BOSHY衍生物，而且阐明了光聚合的反应动力学分析，大大扩展了可见光led作为紫外光的替代品在光聚合中的应用。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.