Solvent Effects on the Intramolecular Charge Transfer Character of N,N-Diaryl Dihydrophenazine Catalysts for Organocatalyzed Atom Transfer Radical Polymerization.
Solvent Effects on the Intramolecular Charge Transfer Character of N,N-Diaryl Dihydrophenazine Catalysts for Organocatalyzed Atom Transfer Radical Polymerization.
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DOI：
10.1002/pola.28574
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发表时间：
2017-09-15
期刊：
影响因子：
--
通讯作者：
Miyake GM
中科院分区：
文献类型：
--
作者：
Ryan MD;Theriot JC;Lim CH;Yang H;Lockwood A;Garrison NG;Lincoln SR;Musgrave CB;Miyake GM
研究了N，N-二芳基二氢吩嗪光催化剂（PC）在不同溶剂中的分子内电荷转移性质，并考察了其在有机催化原子转移自由基聚合（O-ATRP）中的性能.具有计算预测的最低能量激发态的PC表现出电荷转移（CT）特性，可以在宽范围的溶剂极性，从非极性己烷到高极性N，N-二甲基乙酰胺操作高度受控的O-ATRP。对于计算预测的最低能量激发态不具有CT特征的PC，它们操作受控O-ATRP的能力降低。该研究证实了CT特征在N，N-二芳基二氢吩嗪PC的激发态中的重要性，并且对CT PC活性的更深入理解使得能够以受控方式合成低分散度（<1.10）的聚合物。研究了溶剂对N，N-二芳基二氢吩嗪光催化剂激发态性质的影响。获得具有电荷转移特征的最低能量激发态的催化剂能够在宽范围的溶剂极性中操作高度受控的O-ATRP。对这些催化剂活性的进一步理解允许使用五种不同催化剂的一般条件来优化甲基丙烯酸甲酯的O-ATRP。
The nature of intramolecular charge transfer of N,N-diaryl dihydrophenazine photocatalysts (PCs) in different solvents is explored in context of their performance in organocatalyzed atom transfer radical polymerization (O-ATRP). PCs having a computationally predicted lowest energy excited state exhibiting charge transfer (CT) character can operate a highly controlled O-ATRP in a wide range of solvent polarities, from non-polar hexanes to highly polar N,N-dimethylacetamide. For PCs having a computationally predicted lowest energy excited state not possessing CT character, their ability to operate a controlled O-ATRP is decreased. This study confirms the importance of CT character in the excited state for N,N-diaryl dihydrophenazine PCs, and a deeper understanding of the activity of CT PCs has enabled the synthesis of polymers of low dispersity ( < 1.10) in a controlled fashion. The effect of solvent on the nature of the excited states of N,N-diaryl dihydrophenazine photocatalysts has been explored. Catalysts that access a lowest energy excited state having charge transfer character are capable of operating a highly controlled O-ATRP in a wide range of solvent polarities. Further understanding of the activity of these catalysts has allowed for the employment of general conditions across five different catalysts for an optimized O-ATRP of methyl methacrylate.
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21.8
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