Guchhait Chandrakanta, Suriyaa Vembanan, Sahu Nihar, Sarkar Sovik Dey, Adhikari Bimalendu
Department of Chemistry, National Institute of Technology Rourkela, Rourkela, Odisha 769008, India.
Chem Commun (Camb). 2023 Dec 7;59(98):14482-14496. doi: 10.1039/d3cc03659f.
Ferrocene (Fc), a classical organometallic complex, has found potential applications in ligand design, catalysis, and analytical, biological, medicinal and materials chemistry. In recent years, the use of Fc as a building block in supramolecular chemistry has emerged. The molecular shape, size, and hydrophobicity of Fc make it an ideal guest for a variety of macrocyclic host molecules to form stable host-guest complexes. The vertical distance (3.3 Å) between two cyclopentadienyl rings and molecular "ball bearing" property in Fc support the formation of intramolecular π-π stacking, H-bonding and metallophilic interactions between two appropriate substituents in 1,'-disubstituted ferrocenes. Along with these molecular features, the rigidity along with rotational flexibility, redox reversibility and oxidation-triggered tunable hydrophobicity of Fc have led to its use as an exotic building block for the development of a wide range of supramolecular assemblies such as smart molecular receptors, intricate metal-organic assemblies, supramolecular polymers, and gels including out-of-equilibrium assemblies and metal nanoparticle assemblies. This review highlights the concepts behind the design and development of these assemblies, where the Fc unit has a direct and defined role in their formation and function. The use of Fc in supramolecular assembly is still a relatively young field and set to be the subject of increasing research interest towards the development of fascinating supramolecular structures with tailored properties and programmable functions towards applications in materials and biological sciences.
二茂铁（Fc）是一种经典的有机金属配合物，已在配体设计、催化以及分析化学、生物化学、药物化学和材料化学等领域展现出潜在应用价值。近年来，二茂铁作为超分子化学中的一个结构单元开始崭露头角。二茂铁的分子形状、大小和疏水性使其成为各类大环主体分子形成稳定主客体配合物的理想客体。二茂铁中两个环戊二烯基环之间的垂直距离（3.3 Å）以及分子的“滚珠轴承”特性有助于在1,'-二取代二茂铁的两个合适取代基之间形成分子内π-π堆积、氢键和金属亲合相互作用。除了这些分子特征外，二茂铁的刚性与旋转灵活性、氧化还原可逆性以及氧化引发的可调疏水性，使其成为开发多种超分子组装体的奇特结构单元，这些组装体包括智能分子受体、复杂的金属有机组装体、超分子聚合物以及凝胶，其中还包括非平衡组装体和金属纳米颗粒组装体。本综述重点介绍了这些组装体设计与开发背后的概念，其中二茂铁单元在其形成和功能中具有直接且明确的作用。二茂铁在超分子组装中的应用仍是一个相对较新的领域，并且随着人们对开发具有定制性质和可编程功能以应用于材料科学和生物科学的迷人超分子结构的兴趣不断增加，该领域必将成为越来越多研究的主题。
