Structure–property relationships of core-substituted diaryl dihydrophenazine organic photoredox catalysts and their application in O-ATRP
Structure–property relationships of core-substituted diaryl dihydrophenazine organic photoredox catalysts and their application in O-ATRP
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核取代二芳基二氢吩嗪有机光氧化还原催化剂的结构—性能关系及其在O-ATRP中的应用
DOI：
10.1039/d1py01060c
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发表时间：
2021
影响因子：
4.6
通讯作者：
Miyake, Garret M.
中科院分区：
文献类型：
--
作者：
Price, Mariel J.;Puffer, Katherine O.;Kudisch, Max;Knies, Declan;Miyake, Garret M.
光诱导有机催化原子转移自由基聚合(O-ATRP)是一种利用有机光催化剂、低能量可见光驱动的可控自由基聚合技术。O-ATRP的局限性传统上包括需要高催化剂负载量(1000ppm)和可控制聚合的单体范围狭窄。最近的研究表明，N，N-二芳基二氢吩嗪(DHP)有机光还原催化剂(PC)能够在低至10ppm的负载下控制O-ATRP，这是该领域的一个重大进展。在这项工作中，我们合成了五个新的DHP PC，并测试了它们在低ppm催化剂负载下控制O-ATRP的效果。我们发现，我们能够在PC负载量低至10ppm(相对于单体)的情况下聚合甲基丙烯酸甲酯，同时生成分散度低至Đ=1.33的聚合物，并获得接近1的引发剂效率(I*)(102%)。除了将这些PC应用于O-ATRP外，我们还对本文报道的新的DHP PC的结构-性质关系进行了深入的研究，并报道了以前报道的DHP的新的光物理表征数据。我们在这里讨论的DHP结构-性质关系的洞察将有助于阐明它们在低催化剂载量下催化O-ATRP的能力。此外，这项工作揭示了结构修饰如何影响某些PC性能，目的是加强我们对如何调整PC结构的理解，以克服O-ATRP中目前的限制，例如具有挑战性的单体的控制聚合。
Photoinduced organocatalyzed atom-transfer radical polymerization (O-ATRP) is a controlled radical polymerization technique that can be driven using low-energy, visible light and makes use of organic photocatalysts. Limitations of O-ATRP have traditionally included the need for high catalyst loadings (1000 ppm) and the narrow scope of monomers that can be controllably polymerized. Recent advances have shown that N,N-diaryl dihydrophenazine (DHP) organic photoredox catalysts (PCs) are capable of controlling O-ATRP at PC loadings as low as 10 ppm, a significant advancement in the field. In this work we synthesized five new DHP PCs and examined their efficacy in controlling O-ATRP at low ppm catalyst loadings. We found that we were able to polymerize methyl methacrylate at PC loadings as low as 10 ppm (relative to monomer) while producing polymers with dispersities as low as Đ = 1.33 and achieving initiator efficiencies (I*) near unity (102%). In addition to applying these PCs in O-ATRP, we carried out a thorough investigation into the structure–property relationships of the new DHP PCs reported herein and report new photophysical characterization data for previously reported DHPs. The insight into the DHP structure–property relationships that we discuss herein will aid in the elucidation of their ability to catalyze O-ATRP at low catalyst loadings. Additionally, this work sheds light on how structural modifications affect certain PC properties with the goal of bolstering our understanding of how to tune PC structures to overcome current limitations in O-ATRP such as the controlled polymerization of challenging monomers.
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影响因子：
15
作者：
McCarthy BG;Pearson RM;Lim CH;Sartor SM;Damrauer NH;Miyake GM
通讯作者：
Miyake GM
影响因子：
15
作者：
Pearson RM;Lim CH;McCarthy BG;Musgrave CB;Miyake GM
通讯作者：
Miyake GM
影响因子：
5.5
作者：
Corbin DA;McCarthy BG;van de Lindt Z;Miyake GM
通讯作者：
Miyake GM
DOI：
10.1002/pola.28574
发表时间：
2017-09-15
期刊：
Journal of polymer science. Part A, Polymer chemistry
影响因子：
--
作者：
Ryan MD;Theriot JC;Lim CH;Yang H;Lockwood A;Garrison NG;Lincoln SR;Musgrave CB;Miyake GM
通讯作者：
Miyake GM
影响因子：
5.5
作者：
Blaine G. McCarthy;Steven M. Sartor;J. Cole;N. Damrauer;G. Miyake
通讯作者：
Blaine G. McCarthy;Steven M. Sartor;J. Cole;N. Damrauer;G. Miyake