发表机构
Peking University; ShanghaiTech University; School of Physics and Astronomy, Shanghai Jiao Tong University; The Chinese University of Hong Kong (Shenzhen)（北京大学; 上海科技大学; 上海交通大学物理与天文学院; 香港中文大学（深圳））
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本研究提出编码不对称配体BTH，通过金属选择性组装实现二维MOF拓扑多样化，Cu-BTH-MOF电导率比Zn-BTH-MOF高六个数量级。
AI 中文摘要
二维金属有机框架（2D MOFs）具有多样化的拓扑结构，为探索非常规电子和晶格动力学响应提供了强大平台。然而，其结构多样性从根本上受到高对称配体固定几何形状的限制。在此，我们引入一种编码的不对称配体——苯并[b]三亚苯-2,3,6,7,11,12-六醇（BTH），用于金属选择性拓扑组装。通过整合多位点配位场与空间位阻差异化的环境，BTH展现出独特的拓扑可编程性：不同的二价金属离子引导不同的框架结构。具体而言，BTH与二价Cu(II)和Zn(II)离子配位分别组装出具有双模式六方孔拓扑的Cu-BTH-MOF和具有均匀六方通道的Zn-BTH-MOF，这得到了PXRD Pawley精修、结构模拟和孔径分布分析的支持。此外，这种拓扑差异伴随着电荷传输性质的显著差异，其中Cu-BTH-MOF的电导率达到1.186×10⁻³ S cm⁻¹，比Zn-BTH-MOF（3.38×10⁻¹⁰ S cm⁻¹）高出六个数量级以上。这项工作确立了配体去对称化作为一种可编程策略，用于二维MOF中金属选择性拓扑多样化。
英文摘要
Two-dimensional metal-organic frameworks (2D MOFs), with diverse topological architectures, provide a powerful platform for exploring unconventional electronic and lattice-dynamical responses. Yet their structural diversity remains fundamentally constrained by the fixed geometry of high-symmetry ligands. Here, we introduce an encoded asymmetric ligand, benzo[b]triphenylene-2,3,6,7,11,12-hexaol (BTH), for metal-selective topological assembly. By integrating multi-site coordination fields with sterically differentiated environments, BTH exhibits distinct topological programmability: different divalent metal ions direct divergent framework architectures. Specifically, coordination of BTH with divalent Cu(II) and Zn(II) ions assembles Cu-BTH-MOF with a dual-mode hexagonal pore topology and Zn-BTH-MOF with uniform hexagonal channels, respectively, as supported by PXRD Pawley refinement, structural simulations, and pore-size distribution analysis. Furthermore, this topological divergence is accompanied by a significant divergence in charge-transport properties, with Cu-BTH-MOF reaching an electrical conductivity of 1.186 x 10-3 S cm-1, more than six orders of magnitude higher than that of Zn-BTH-MOF (3.38 x 10-10 S cm-1). This work establishes ligand desymmetrization as a programmable strategy for metal-selective topological diversification in 2D MOFs.
