Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
The Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science and Technology, Kowloon, Hong Kong 999077, China.
Dalton Trans. 2023 Feb 14;52(7):1913-1918. doi: 10.1039/d2dt03382h.
In this work, a series of butterfly-like isomers named oxacalix[2]naphthalene[2]pyrazine (ONP) were conveniently synthesized by a one-step catalyst-free reaction in a facile manner, and they exhibit typical characteristics of aggregation-induced emission (AIE). The mechanism study shows that restriction of intramolecular vibration (RIV) is the reason for their AIE properties. The pyrazine groups endow ONP molecules with good coordination ability, which makes them ideal ligands for constructing metal-organic frameworks (MOFs). Thus, three ONP-based luminescent MOFs were constructed, and they exhibit intense emission with lifetimes in the order of microseconds. More importantly, different ONP isomers have different binding capacities, and thus only one kind of MOF can be obtained even when using an isomer mixture of ONP ligands. This result suggested that the conformation of ONPs is an important determining factor for their application as bridging ligands. This work not only reports a series of new RIV-type AIEgens, but also offers a new platform for the construction of luminescent MOFs.
在这项工作中，通过简便的一步无催化剂反应方便地合成了一系列命名为氧杂杯[2]萘[2]吡嗪（ONP）的蝶状异构体，它们表现出典型的聚集诱导发光（AIE）特性。机理研究表明，分子内振动的限制（RIV）是它们 AIE 特性的原因。吡嗪基团赋予 ONP 分子良好的配位能力，使其成为构建金属-有机骨架（MOFs）的理想配体。因此，构建了三种基于 ONP 的发光 MOFs，它们具有强烈的发射，寿命在微秒级。更重要的是，不同的 ONP 异构体具有不同的结合能力，因此即使使用 ONP 配体的异构体混合物，也只能得到一种 MOF。该结果表明，ONP 的构象是其作为桥联配体应用的一个重要决定因素。这项工作不仅报道了一系列新的 RIV 型 AIEgens，还为构建发光 MOFs 提供了一个新的平台。
