Jiang Hao, Jia Jiangtao, Shkurenko Aleksander, Chen Zhijie, Adil Karim, Belmabkhout Youssef, Weselinski Lukasz J, Assen Ayalew H, Xue Dong-Xu, O'Keeffe Michael, Eddaoudi Mohamed
Functional Materials Design, Discovery and Development Research Group (FMD3), Advanced Membranes and Porous Materials Center (AMPMC), Division of Physical Sciences and Engineering (PSE) , King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900 , Kingdom of Saudi Arabia.
School of Molecular Sciences , Arizona State University , Tempe , Arizona 85287 , United States.
J Am Chem Soc. 2018 Jul 18;140(28):8858-8867. doi: 10.1021/jacs.8b04745. Epub 2018 Jul 5.
Rational design and construction of metal-organic frameworks (MOFs) with intricate structural complexity are of prime importance in reticular chemistry. We report our latest addition to the design toolbox in reticular chemistry, namely the concept of merged nets based on merging two edge-transitive nets into a minimal edge-transitive net for the rational construction of intricate mixed-linker MOFs. In essence, a valuable net for design enclosing two edges (not related by symmetry) is rationally generated by merging two edge-transitive nets, namely (3,6)-coordinated spn and 6-coordinated hxg. The resultant merged-net, a (3,6,12)-coordinated sph net with net transitivity [32] enclosing three nodes and two distinct edges, offers potential for deliberate design of intricate mixed-linker MOFs. We report implementation of the merged-net approach for the construction of isoreticular rare-earth mixed-linker MOFs, sph-MOF-1 to -4, based on the assembly of 12-c hexanuclear carboxylate-based molecular building blocks (MBBs), displaying cuboctahedral building units, 3-c tritopic ligands, and 6-c hexatopic ligands. The resultant sph-MOFs represent the first examples of MOFs where the underlying net is merged from two 3-periodic edge-transitive nets, spn and hxg. Distinctively, the sph-MOF-3 represents the first example of a mixed-linker MOF to enclose both trigonal and hexagonal linkers. The merged-nets approach allows the logical practice of isoreticular chemistry by taking into account the mathematically correlated dimensions of the two ligands to afford the deliberate construction of a mixed-linker mesoporous MOF, sph-MOF-4. The merged-net equation and two key parameters, ratio constant and MBB constant, are disclosed. A merged-net strategy for the design of mixed-linker MOFs by strictly controlling the size ratio between edges is introduced.
合理设计和构建具有复杂结构复杂性的金属有机框架（MOF）在网状化学中至关重要。我们报告了我们在网状化学设计工具箱中的最新成果，即基于将两个边传递网络合并为一个最小边传递网络的合并网络概念，用于合理构建复杂的混合连接体MOF。本质上，通过合并两个边传递网络，即（3,6）配位的spn和6配位的hxg，合理生成了一个用于设计的包含两条边（非对称相关）的有价值网络。所得的合并网络是一个具有网络传递性[32]的（3,6,12）配位的sph网络，包含三个节点和两条不同的边，为复杂混合连接体MOF的精心设计提供了潜力。我们报告了基于12-c六核羧酸根基团分子构建块（MBB）的组装，实现了合并网络方法用于构建同构稀土混合连接体MOF，即sph-MOF-1至-4，展示了立方八面体构建单元、3-c三齿配体和6-c六齿配体。所得的sph-MOF代表了MOF的首个实例，其基础网络是由两个3周期边传递网络spn和hxg合并而成。独特的是，sph-MOF-3代表了第一个同时包含三角形和六边形连接体的混合连接体MOF实例。合并网络方法通过考虑两种配体的数学相关维度，允许进行同构化学的逻辑实践，以实现混合连接体介孔MOF，即sph-MOF-4的精心构建。公开了合并网络方程以及两个关键参数，即比例常数和MBB常数。引入了一种通过严格控制边之间的尺寸比来设计混合连接体MOF的合并网络策略。
