Molecular crystals displaying elastic flexibility have important applications in the fields of optoelectronics and nanophotonic technologies. Understanding the mechanisms by which these materials bend is critical to the design of future materials incorporating these properties. Based on the known elastic properties of bis(acetylacetonato)copper(II), a series of 14 aliphatic derivatives are synthesized and crystallized. All those which grew in a needle morphology display noticeable elasticity, with 1D chains of π‐stacked molecules parallel to the long metric length of the crystal a consistent crystallographic feature. Crystallographic mapping is used to measure the mechanism of elasticity at an atomic‐scale. Symmetric derivatives with ethyl and propyl side chains are found to have different mechanisms of elasticity, which are further distinguished from the previously reported mechanism of bis(acetylacetonato)copper(II). While crystals of bis(acetylacetonato)copper(II) are known to bend elastically via a molecular rotation mechanism, the elasticity of the compounds presented is facilitated by expansion of their π‐stacking interactions.

Metal–organic frameworks (MOFs) are emerging porous materials with highly tunable structures developed in the 1990s, while organometallic chemistry is of fundamental importance for catalytic transformation in the academic and industrial world for many decades. Through the years, organometallic chemistry has been incorporated into functional MOF construction for diverse applications. Here, we will focus on how organometallic chemistry is applied in MOF design and modifications from linker-centric and metal-cluster-centric perspectives, respectively. Through structural design, MOFs can function as a tailorable platform for traditional organometallic transformations, including reaction of alkenes, cross-coupling reactions, and C–H activations. Besides, an overview will be made on other application categories of organometallic MOFs, such as gas adsorption, magnetism, quantum computing, and therapeutics.

MOF-derived carbons are a class of porous material that combine the stability of porous carbon with the functionality and versatility of MOFs. This review describes the systematic design, characterization, and application of these materials.