Self‐assembly of bis‐picolyl‐appended calix[4]arene (L) with Cu^I or Cu^II salts resulted in a collection of multinuclear architectures capable of expressing structural reconfigurations in response to various chemical stimuli: addition of copper salt, solvents, or oxidation. Coordination of L to CuX (X=Br, I) selectively yielded dinuclear macrocycles Cu^I₂L₂Br₂ (1) and Cu^I₂L₂I₂ (3) that were transformed into tetranuclear assemblies Cu^I₄L₂Br₄ (2) and Cu^I₄L₂I₄ (4) upon further addition of CuX. These supramolecules persist as robust and discrete entities in solution that display red emission; notably, 4 exhibits luminescence thermochromism. Assembly of L with CuCl₂ produced macrocycle Cu^II₂L₂Cl₄ (5), which crystallised as cage [Cu^II₂L₄(μ‐Cl)]³⁺ (6) in the presence of MeOH. Two chemical signals—introduction of CuCl₂ and addition of CH₃CN—regenerated macrocycle 5. Coordination of L to Cu(OTf) yielded macrocycle Cu^I₂L₂(OTf)₂ (7) that also crystallised as cage 6 upon oxidation in CHCl₃.

中文翻译：

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化学响应性铜-lix芳烃体系结构的转变

将带有双吡啶甲基的杯[4]亚芳基（L）与Cu ^I或Cu ^II盐进行自组装，形成了多核结构的集合，这些结构能够响应各种化学刺激而表达结构重构：添加铜盐，溶剂，或氧化。的协调大号到的CuX（X = Br的，I）选择性地得到双核大环化合物的Cu^我₂大号₂溴₂（1）和铜^我₂大号₂我₂（3），其被转化到四核组件的Cu^我₄进一步添加CuX时，L ₂ Br ₄（2）和Cu ^I ₄ L ₂ I ₄（4）。这些超分子在显示红色发射的溶液中以健壮和离散的实体形式存在。值得注意的是，4表现出发光热致变色。L与CuCl _2的组装产生了大环Cu ^II ₂ L ₂ Cl ₄（5），其结晶为笼状[Cu ^II ₂ L ₄（μ-Cl）] ³⁺（6）在MeOH的存在下。引入CuCl ₂和添加CH ₃ CN这两个化学信号再生了大环5。的协调大号成Cu（OTF）产生的大环化合物的Cu^我₂大号₂（OTF）₂（7），其还结晶为笼6在CHCl氧化后₃。