The kinetics of photoinduced copper(I) catalyzed azide–alkyne cycloaddition (CuAAC) polymerizations were assessed as a function of copper(II) amine-based ligands. Copper(II) bromide ligated with 1,1,4,7,10,10-hexamethylenetetramine (HMTETA) exhibited the fastest kinetics in both Norrish type(I) and type(II) photoinitiating systems. A characteristic induction period is observed with these polymerizations and is manipulated by adding an external tertiary amine in Norrish Type(II) photoinitiating systems or by changing the anion of the copper(II) salt. Halides, specifically bromide and chloride, exhibit the fastest kinetics with the smallest induction period in comparison with organic anions, such as bistriflimide and triflate. The temporal control of the photo-CuAAC polymerization is affected by pre-ligation of the copper catalyst, by the presence of certain anions such as acetate, and by specific ligands such as tetramethylethylenediamine (TMEDA).

中文翻译：

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铜配体和阴离子效应：控制光引发铜(i)催化叠氮化物-炔环加成聚合的动力学†

光诱导铜（I ）催化叠氮化物-炔烃环加成（CuAAC）聚合的动力学被评估为铜（ II）胺基配体的函数。与 1,1,4,7,10,10-六亚甲基四胺 (HMTETA) 连接的溴化铜 ( II )在 Norrish 型 (I) 和型 (II) 光引发体系中表现出最快的动力学。在这些聚合中观察到特征诱导期，并通过在 Norrish Type(II) 光引发体系中添加外部叔胺或通过改变铜 ( II ) 盐的阴离子来控制诱导期。与有机阴离子（例如双氟甲酰亚胺和三氟甲磺酸盐）相比，卤化物（特别是溴化物和氯化物）表现出最快的动力学和最短的诱导期。光-CuAAC聚合的时间控制受到铜催化剂的预连接、某些阴离子（例如乙酸根）的存在以及特定配体（例如四甲基乙二胺（TMEDA））的影响。