College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450001, P.R. China.
College of Chemistry and Chemical Engineering, Henan Polytechnic University Henan Key Laboratory of, Coal Green Conversion, Henan Polytechnic University, Jiaozuo, 454000, P.R. China.
Chemistry. 2019 Mar 1;25(13):3376-3381. doi: 10.1002/chem.201805808. Epub 2019 Feb 13.
Silver chalcogenolate clusters (SCCs) and silver cluster-assembled materials (SCAMs) are an important category of novel luminescent materials, the emission of which can be modulated by variation of the cluster nodes and linker species. Here, the successfully synthesis of two isostructural 2D SCAMs is reported: Ag bpa and Ag bpe are formed by using two linkers with different conformational freedom (bpa=1,2-bis(4-pyridyl)ethane, bpe=1,2-bis(4-pyridyl)ethylene), with dodenuclear silver chalcogenolate clusters as secondary building units (SBUs). Interestingly, nonluminescent Ag bpa at room temperature could quickly transform into 1D Ag bpa, with concomitant dissociation of two silver atoms and the remaining ten silver atoms rearranging in the cluster, thus exhibiting an intense yellow phosphorescence after being triggered by acetonitrile (CH CN). Similarly, stimulating Ag bpe with CH CN, by contrast, gave another 2D structure Ag bpe-1b with the distorted SBUs and different topology structure, and both of them are merely red-emissive at low temperature. To note, after exchanging ligands, room-temperature nonluminescent 2D Ag bpe-1b can be transformed into intensely luminescent 1D Ag bpa. This linker-flexibility-dependent structural transformation and cluster-based SBU controlled luminescence remains scarce. Our work provides new insights into structure-luminescence relationship in clustered metal-organic frameworks and intelligent stimulus-responsive luminescent materials.
银硫属团簇（SCCs）和银簇组装材料（SCAMs）是一类重要的新型发光材料，其发光可以通过改变簇节点和连接体种类来调节。在此，报道了两种同构的 2D SCAMs 的成功合成：Ag bpa 和 Ag bpe 是通过使用两个具有不同构象自由度的连接体（bpa=1,2-双（4-吡啶基）乙烷，bpe=1,2-双（4-吡啶基）乙烯）形成的，其中多核银硫属团簇作为次级建筑单元（SBUs）。有趣的是，室温下非发光的 Ag bpa 可以快速转化为 1D Ag bpa，同时有两个银原子解离，其余十个银原子在簇中重新排列，因此在被乙腈（CH3CN）触发后呈现出强烈的黄色磷光。同样，用 CH3CN 刺激 Ag bpe ，与之相反，得到了另一个具有扭曲 SBUs 和不同拓扑结构的 2D 结构 Ag bpe-1b，它们在低温下均仅发红光。值得注意的是，在交换配体后，室温下非发光的 2D Ag bpe-1b 可以转化为强发光的 1D Ag bpa。这种依赖于连接体灵活性的结构转变和基于簇的 SBU 控制发光在以前的研究中很少见。我们的工作为聚集金属-有机框架和智能刺激响应发光材料的结构-发光关系提供了新的见解。
