Rational Use of Aromatic Solvents for Direct Arylation Polycondensation: C-H Reactivity versus Solvent Quality.
Rational Use of Aromatic Solvents for Direct Arylation Polycondensation: C-H Reactivity versus Solvent Quality.
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DOI：
10.1021/acsmacrolett.5b00783
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发表时间：
2015-11
影响因子：
5.8
通讯作者：
Rukiya Matsidik;H. Komber;M. Sommer
中科院分区：
文献类型：
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作者：
Rukiya Matsidik;H. Komber;M. Sommer
直接芳基化缩聚（DAP）的溶剂至关重要。对于溶解度降低的共轭聚合物，溶剂的选择决定了可以达到的最大分子量，因此，通常需要良好的芳香族溶剂。然而，在 DAP 条件下，芳香族溶剂中存在的 C-H 键的无意激活会导致原位溶剂终止，从而与逐步生长竞争。在这里，我们评估了七种芳香族溶剂对不同溶解度的无缺陷萘二酰亚胺 (NDI) 基共聚物的 DAP 的相对 C-H 反应性和溶剂质量。随着氯和甲基取代基取代度的增加，C-H 反应性大大降低。均三甲苯在很大程度上是 C-H 不反应性的，因此，尽管是一种温和的溶剂，但对于溶解度有限的 NDI 共聚物来说，在高温下能够实现非常高的分子量。
The solvent for direct arylation polycondensation (DAP) is of crucial importance. For conjugated polymers exhibiting reduced solubility, the choice of solvent decides on the maximum molecular weight that can be achieved, hence, good aromatic solvents are generally desirable. However, unintentional activation of C-H bonds present in aromatic solvents under DAP conditions leads to in situ solvent termination which competes with step growth. Here we evaluate relative C-H reactivity and solvent quality of seven aromatic solvents for the DAP of defect-free naphthalene diimide (NDI)-based copolymers of different solubility. C-H reactivity is strongly reduced with increasing degree of substitution for both chlorine and methyl substituents. Mesitylene is largely C-H unreactive and, thus, albeit being a moderate solvent, enables very high molecular weights at elevated temperature for NDI copolymers with limited solubility.