Taking advantage of V‐shaped ligands, a Zn^II metallocryptand, namely {[Zn₂(didp)₂(m‐bdc)₂]}_n, (1) [didp = 2,8‐di(1H‐imidazol‐1‐yl)‐dibenzothiophene and m‐H₂bdc = isophthalic acid], has been hydrothermally synthesized. Single‐crystal X‐ray diffraction analysis reveals a 26‐membered butterfly‐type metallomacrocycle [Zn₂(didp)₂]. One m‐bdc²⁻ ligand bridges [Zn₂(didp)₂] units to form a laterally non‐symmetric [Zn₂(didp)₂(m‐bdc)] metallocryptand with an exo–exo conformation. Another crystallographically independent m‐bdc²⁻ functions as a secondary synthon to bridge discrete metallocryptands into a 1D zigzag chain architecture. Undoubtedly, the choice of two matched ligands in this work is crucial for metallocryptand construction and structure expansion. Interestingly, a rare helical chain with two flexures in one single L and/or R strand is observed. Another important feature is the C—O…π interactions, by which the dimensionality extension of (1) can be induced. Fluorescence measurements and density functional theory (DFT) calculations illustrate that the emission of (1) can probably be attributed to ligand‐to‐ligand charge transfer (LLCT).

中文翻译：

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由V型二咪唑结构单元诱导的具有前所未有的双挠螺旋的新型ZnII金属密码子。

利用V形配体的优势，Zn ^II金属密码子，即{[Zn ₂（didp）₂（m- bdc）₂ ]} _n，（1）[didp = 2,8-di（1 H -imidazol-1） -yl）-dibenzothiophene和m- H ₂ bdc =间苯二甲酸]，已经水热合成。X射线单晶衍射分析揭示了一个26元的蝴蝶型金属大环[Zn ₂（didp）₂ ]。一个m -bdc ^2-配体桥[Zn ₂（didp）₂ ]单元形成侧向非对称[Zn ₂（didp）₂（m -bdc）]金属密码子，具有exo-exo构象。另一个在晶体学上独立的m- bdc ^2-充当次级合成子，将离散的金属密码子桥接到一维之字形链架构中。毫无疑问，这项工作中两个匹配配体的选择对于金属密码结构和结构扩展至关重要。有趣的是，罕见的螺旋链在一个L和/或R中具有两个弯曲链被观察到。另一个重要特征是C-O…π相互作用，由此可诱导（1）的尺寸扩展。荧光测量和密度泛函理论（DFT）计算表明（1）的发射可能归因于配体到配体的电荷转移（LLCT）。