Osmium metal complex based on photoinduced electron transfer for broad-wavelength-responsive free-radical and cationic photopolymerization

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry Pub Date : 2026-07-21 DOI:10.1039/d6py00459h

Guohao Han,Yihao Sun,Tianyi Han,Guanghui An,Yi Zhu

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引用次数: 0

Abstract

The internal shielding effect of photoinitiators (PI) and the strong Rayleigh scattering of ultraviolet (UV) light limit the depth of polymerization and performance of polymer materials; thus, developing a long-wavelength-responsive photoinitiating system (PIS), especially a near-infrared (NIR)-responsive one, is an important research direction in the field of photopolymerization. In this work, we report two multiband (UV-Visible-NIR)-absorbing PISs composed of osmium metal complexes, diphenyliodonium hexafluorophosphate (Iod) and N-vinylcarbazole (NVK). Steady-state photolysis, electrochemistry and electron spin resonance (ESR) experiments indicated that the active species that initiate photopolymerization were generated through a photoinduced electron transfer (PET) mechanism. Photopolymerization kinetics experiments showed that the osmium PIS can initiate free radical polymerization (FRP) efficiently under LED@365/405/450/535/635/690 nm irradiation. At the same time, they can also initiate cationic polymerization under LED@365/405 nm irradiation. Under laser@690 nm irradiation, our PISs can achieve deep curing (230 mm) of acrylic monomers; they can also successfully achieve polymerization of acrylic monomers under sunlight, demonstrating promising potential applications in deep curing, 3D printing and solar photopolymerization.

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基于光诱导电子转移的锇金属配合物在波长响应自由基和阳离子光聚合中的应用

光引发剂（PI）的内部屏蔽效应和紫外线（UV）的强瑞利散射限制了聚合物材料的聚合深度和性能；因此，开发长波长响应型光引发系统，特别是近红外响应型光引发系统是光聚合领域的一个重要研究方向。在这项工作中，我们报道了两种多波段（紫外可见-近红外）吸收的金属锇配合物，二苯六氟磷酸二苯碘铵（Iod）和n -乙烯基咔唑（NVK）。稳态光解、电化学和电子自旋共振（ESR）实验表明，引发光聚合的活性物质是通过光致电子转移（PET）机制产生的。光聚合动力学实验表明，在LED@365/405/450/535/635/690 nm辐照下，PIS锇能有效引发自由基聚合（FRP）。同时，在LED@365/405 nm辐照下，它们还能引发阳离子聚合。在laser@690 nm照射下，我们的PISs可以实现丙烯酸单体的深度固化（230 mm）；它们还可以在阳光下成功地实现丙烯酸单体的聚合，在深度固化、3D打印和太阳能光聚合方面显示出有前景的应用前景。

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来源期刊

Polymer Chemistry POLYMER SCIENCE-

CiteScore

8.60

自引率

8.70%

发文量

535

审稿时长

1.7 months

期刊介绍： Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.