Functional Materials Design, Discovery and Development Research Group (FMD3), Advanced Membranes and Porous Materials Center (AMPMC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia.
Faraday Discuss. 2017 Sep 8;201:127-143. doi: 10.1039/c7fd00119c.
Highly-connected and minimal edge-transitive nets (with one or two kinds of edge) can be regarded as ideal blueprints for the rational design and construction of metal-organic frameworks (MOFs). Here we report and affirm the prominence of highly-connected nets as suitable targets in reticular chemistry for the design and synthesis of MOFs. Of special interest are augmented highly-connected binodal edge-transitive nets embedding a unique and precise positioning and connectivity of the net vertex figures, regarded as net-coded building units (net-cBUs). Explicitly, a definite net-cBU encompasses precise geometrical information that codes a selected net uniquely and matchlessly, a compelling perquisite for the rational design of MOFs. Interestingly, the double six-membered ring (d6R) building unit offers great potential to be used as a net-cBU for the deliberate reticulation of the sole two edge-transitive nets with a vertex figure as a d6R, namely the (4,12)-coordinated shp net (square and hexagonal prism) and the (6,12)-coordinated alb net (aluminium diboride, hexagonal prism and trigonal prism). We envisioned and proposed various MOF structures based on the derived shp and alb nets. Gaining access to the requisite net-cBUs is essential for the successful practice of reticular chemistry; correspondingly organic and inorganic chemistries were deployed to afford concomitant molecular building blocks (MBBs) with the looked-for shape and connectivity. Practically, the combination of the 12-connected (12-c) rare-earth (RE) polynuclear, points of extension matching the 12 vertices of the hexagonal prism (d6R) with a 4-connected tetracarboxylate ligand or a 6-connected hexacarboxylate ligand afforded the targeted shp-MOF or alb-MOF, respectively. A dodecacarboxylate ligand can be conceived as, and is shown to be, a compatible 12-c MBB, plausibly affording the positioning of the carbon centers of the twelve carboxylate groups on the vertices of the desired hexagonal prism building unit, and combined with the complementary 4-c copper paddlewheel [Cu(OC-)] cluster or 6-c metal trinuclear [MO(OC-)] clusters/zinc tetranulcear [ZnO(OC-)] clusters to credibly afford the construction of new MOF structures with underlying topologies based on derived shp and alb nets.
高度连接和最小边传递网络（具有一种或两种类型的边）可以被视为合理设计和构建金属有机骨架（MOF）的理想蓝图。在这里，我们报告并肯定了高度连接的网络作为网状化学中设计和合成 MOF 的合适目标的突出地位。特别有趣的是，扩充的高度连接的双节点边传递网络嵌入了网络顶点图的独特而精确的定位和连接，被视为网络编码构建单元（net-cBU）。明确地说，一个确定的 net-cBU 包含精确的几何信息，该信息唯一且无与伦比地对所选网络进行编码，这是 MOF 合理设计的必要条件。有趣的是，双六元环（d6R）构建单元具有很大的潜力，可以用作唯一具有顶点图为 d6R 的两个边传递网络（即（4,12）配位 shp 网络（正方形和六方棱柱）和（6,12）配位 alb 网络（六方棱柱和三角棱柱）的 deliberate reticulation 的 net-cBU。我们基于衍生的 shp 和 alb 网络设想并提出了各种 MOF 结构。获得所需的 net-cBU 对于成功实践网状化学至关重要；相应地，有机和无机化学被部署以提供具有所需形状和连接的伴随分子构建块（MBB）。实际上，12 连接（12-c）稀土（RE）多核的组合，扩展点与六方棱柱（d6R）的 12 个顶点匹配，带有 4 连接的四羧酸配体或 6 连接的六羧酸配体，分别提供目标 shp-MOF 或 alb-MOF。十二羧酸配体可以被设想为并且被证明是一种相容的 12-c MBB，可能提供所需六方棱柱构建单元顶点上十二个羧酸基团的碳原子的定位，并与互补的 4-c 铜桨轮[Cu（OC-）]簇或 6-c 金属三核[MO（OC-）]簇/锌四核[ZnO（OC-）]簇结合，可合理地提供基于衍生的 shp 和 alb 网络的拓扑结构的新 MOF 结构的构建。
