Electronic substituent effects on ketocoumarin-based photoinitiators: Structure-activity relationships for high-efficiency LED photopolymerization

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings Pub Date : 2025-03-17 DOI:10.1016/j.porgcoat.2025.109229

Shuheng Fan , Xun Sun , Haipeng Liu , Xue Qi , Jingjing Lou , Peike Wang , Yulian Pang , Yingquan Zou , Jun Wei

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引用次数: 0

Abstract

Ketocoumarins have emerged as promising candidates for efficient Norrish type II photoinitiators (PIs) due to their long light absorption wavelengths, excellent photosensitive activity, and high photoinduced electron transfer efficiency. In this study, a series of ketocoumarin-based PIs (KCs) were designed and synthesized with various substituents, including methyl, trifluoromethyl, hydroxyl, phenyl, p-methylaminophenyl, and p-methylthiophenyl, linked to carbonyl. The primary objective was to explore the structure-reactivity-efficiency relationships of KCs, which are crucial for LED photopolymerization. The introduction of electron-withdrawing groups linked to carbonyl resulted in a relative redshift in absorption and enhanced photoinitiation efficiency in KCs. In contrast, the incorporation of electron-donating groups led to a blueshift in absorption or significant changes due to alterations in the chromophore's functional structure. These effects were confirmed through theoretical calculations. Notably, S-KC-F, with carbonyl connected to trifluoromethyl, exhibited superior photoinitiation performance, surpassing that of commercial PIs KC-01 and ITX under UV-LED irradiation. Additionally, S-KC-F exhibited good solubility, suggesting its potential for practical applications; however, its poor cytocompatibility may restrict its use in food packaging and biomedicine. These findings provide a strategic approach to designing high-performance PIs.

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酮香豆素基光引发剂的电子取代效应：高效LED光聚合的构效关系

酮香豆素具有较长的光吸收波长、优异的光敏活性和较高的光致电子转移效率，是高效的Norrish II型光引发剂（pi）的有希望的候选者。本研究设计并合成了一系列以酮香豆素为基础的pi (KCs)，其取代基包括甲基、三氟甲基、羟基、苯基、对甲基氨基苯基和对甲基噻吩基，并与羰基相连。主要目的是探索KCs的结构-反应性-效率关系，这对LED光聚合至关重要。引入与羰基相连的吸电子基团导致了KCs吸收的相对红移和光引发效率的提高。相比之下，给电子基团的加入导致了吸收中的蓝移或由于发色团功能结构的改变而引起的显著变化。这些效应通过理论计算得到了证实。值得注意的是，在UV-LED照射下，羰基与三氟甲基连接的S-KC-F表现出优越的光引发性能，超过了商用pi KC-01和ITX。此外，S-KC-F具有良好的溶解性，表明其具有实际应用潜力；但由于其细胞相容性差，限制了其在食品包装和生物医药领域的应用。这些发现为设计高性能pi提供了一种战略方法。

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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来源期刊

Progress in Organic Coatings 工程技术-材料科学：膜

CiteScore

11.40

自引率

15.20%

发文量

577

审稿时长

48 days

期刊介绍： The aim of this international journal is to analyse and publicise the progress and current state of knowledge in the field of organic coatings and related materials. The Editors and the Editorial Board members will solicit both review and research papers from academic and industrial scientists who are actively engaged in research and development or, in the case of review papers, have extensive experience in the subject to be reviewed. Unsolicited manuscripts will be accepted if they meet the journal''s requirements. The journal publishes papers dealing with such subjects as: • Chemical, physical and technological properties of organic coatings and related materials • Problems and methods of preparation, manufacture and application of these materials • Performance, testing and analysis.