Department of Chemistry, Texas A&M University, College Station, TX 77842-3012, USA.
Chem Soc Rev. 2014 Aug 21;43(16):5561-93. doi: 10.1039/c4cs00003j.
Metal-organic frameworks (MOFs) are constructed from metal ions/clusters coordinated by organic linkers (or bridging-ligands). The hallmark of MOFs is their permanent porosity, which is frequently found in MOFs constructed from metal-clusters. These clusters are often formed in situ, whereas the linkers are generally pre-formed. The geometry and connectivity of a linker dictate the structure of the resulting MOF. Adjustments of linker geometry, length, ratio, and functional-group can tune the size, shape, and internal surface property of a MOF for a targeted application. In this critical review, we highlight advances in MOF synthesis focusing on linker design. Examples of building MOFs to reach unique properties, such as unprecedented surface area, pore aperture, molecular recognition, stability, and catalysis, through linker design are described. Further search for application-oriented MOFs through judicious selection of metal clusters and organic linkers is desirable. In this review, linkers are categorized as ditopic (Section 1), tritopic (Section 2), tetratopic (Section 3), hexatopic (Section 4), octatopic (Section 5), mixed (Section 6), desymmetrized (Section 7), metallo (Section 8), and N-heterocyclic linkers (Section 9).
金属-有机骨架（MOFs）由金属离子/簇通过有机配体（或桥联配体）配位构建而成。MOFs 的显著特点是其永久孔隙率，这在由金属簇构建的 MOFs 中经常发现。这些簇通常是原位形成的，而配体通常是预先形成的。配体的几何形状和连接性决定了所得 MOF 的结构。通过调整配体的几何形状、长度、比例和官能团，可以调节 MOF 的尺寸、形状和内部表面性质，以满足特定的应用需求。在这篇评论中，我们重点介绍了基于配体设计的 MOF 合成方面的进展。通过配体设计构建 MOF 以获得独特性能的例子，如前所未有的表面积、孔径、分子识别、稳定性和催化性能，都进行了描述。通过明智地选择金属簇和有机配体，进一步寻找面向应用的 MOF 是可取的。在这篇综述中，配体被分类为双齿（第 1 节）、三齿（第 2 节）、四齿（第 3 节）、六齿（第 4 节）、八齿（第 5 节）、混合（第 6 节）、非对称（第 7 节）、金属（第 8 节）和 N-杂环配体（第 9 节）。
