Anorganische Chemie II - Organometallics and Materials, Ruhr-Universität Bochum, Universitätsstr. 150, D-44801 Bochum, Germany.
Chem Soc Rev. 2014 Aug 21;43(16):6062-96. doi: 10.1039/c4cs00101j.
Advances in flexible and functional metal-organic frameworks (MOFs), also called soft porous crystals, are reviewed by covering the literature of the five years period 2009-2013 with reference to the early pertinent work since the late 1990s. Flexible MOFs combine the crystalline order of the underlying coordination network with cooperative structural transformability. These materials can respond to physical and chemical stimuli of various kinds in a tunable fashion by molecular design, which does not exist for other known solid-state materials. Among the fascinating properties are so-called breathing and swelling phenomena as a function of host-guest interactions. Phase transitions are triggered by guest adsorption/desorption, photochemical, thermal, and mechanical stimuli. Other important flexible properties of MOFs, such as linker rotation and sub-net sliding, which are not necessarily accompanied by crystallographic phase transitions, are briefly mentioned as well. Emphasis is given on reviewing the recent progress in application of in situ characterization techniques and the results of theoretical approaches to characterize and understand the breathing mechanisms and phase transitions. The flexible MOF systems, which are discussed, are categorized by the type of metal-nodes involved and how their coordination chemistry with the linker molecules controls the framework dynamics. Aspects of tailoring the flexible and responsive properties by the mixed component solid-solution concept are included, and as well examples of possible applications of flexible metal-organic frameworks for separation, catalysis, sensing, and biomedicine.
柔性和功能化金属-有机骨架（MOFs）的进展，也称为软多孔晶体，通过参考 2009-2013 年五年期间的文献以及 20 世纪 90 年代后期的早期相关工作进行综述。柔性 MOFs 将配位网络的晶体有序性与协同结构可变性相结合。通过分子设计，这些材料可以以可调的方式对各种物理和化学刺激做出响应，而其他已知的固态材料则不存在这种响应。其中引人入胜的性质包括所谓的呼吸和膨胀现象，这是主体-客体相互作用的功能。相转变是由客体吸附/解吸、光化学、热和机械刺激触发的。MOFs 的其他重要柔性性质，如连接子旋转和子网络滑动，虽然不一定伴随着晶体相转变，但也简要提及。重点放在审查原位表征技术的最新进展以及理论方法的结果，以表征和理解呼吸机制和相转变。所讨论的柔性 MOF 系统按所涉及的金属节点的类型以及它们与连接子分子的配位化学如何控制框架动力学进行分类。通过混合成分固溶体概念定制柔性和响应性的方面也包括在内，以及柔性金属-有机骨架在分离、催化、传感和生物医学方面的可能应用的实例。
