Conspectus Covalent organic frameworks (COFs) represent a novel type of crystalline porous polymers with potential applications in many areas. Considering their covalent connectivity in different dimensions, COFs are classified as two-dimensional (2D) layered structures or three-dimensional (3D) networks. In particular, 3D COFs have gained increasing attention recently because of their remarkably large surface areas (>5000 m2/g), hierarchical nanopores and numerous open sites. However, it has been proven to be a major challenge to construct 3D COFs, as the main driving force for their synthesis comes from the formation of covalent bonds. In addition, there are several stones on the roads blocking the development of 3D COFs. First, the successful topology design strategies of 3D COFs have been limited to [4 + 2] or [4 + 3] condensation reactions of the tetrahedral molecules with linear or triangular building blocks in the first decade, which led to only three available topologies (ctn, bor, and dia) and strongly restricted the incorporation of some important functional units. Next, as it is very challenging to obtain large-size single crystals of 3D COFs and the same building blocks may yield many possible structures that are quite difficult to identify from simulations, their structure determination has been considered a major issue. Last, the building blocks utilized to synthesize 3D COFs are very limited, which further affects their functionalization and applications. Therefore, since it was first announced in 2007, research studies regarding 3D COFs have been underexplored for many years, and very few examples have been reported. To confront these obstacles in 3D COFs, we started contributing to this field in 2016. Considering that many interesting quadrilateral molecules (e.g., pyrene and porphyrin) cannot be easily derivatized into linear or triangular motifs, we developed a novel topology design strategy to construct 3D COFs via [4 + 4] condensation reactions of tetrahedral and quadrilateral building blocks. After many trials, we found that this is a general synthetic strategy to build 3D COFs with the new pts topology. In addition, we explored the structure determination of polycrystalline 3D COFs prepared by our developed strategy via a 3D electron diffraction technique. Moreover, we expanded the toolbox of molecular building blocks for creating 3D COFs and successfully demonstrated the functionalization of 3D COFs with characteristic properties and applications. In this Account, we summarize our above ongoing research contributions, including (i) a novel topology design strategy for the synthesis of 3D COFs; (ii) attempts to determine the crystal structure of polycrystalline 3D COFs with atomic resolution; and (iii) the diversification of building blocks and applications of functionalized 3D COFs. Overall, our studies not only offer a new paradigm of expansion in the topology design strategy and building block families of 3D COFs, but also provide an idea of future opportunities for relevant researchers ...

A simple strategy to construct a stimuli-responsive mechanized zirconium metal-organic framework for on-command cargo release.

By taking advantage of large changes in geometric and electronic structure during the reversible trans – cis isomerisation, azobenzene derivatives have been widely studied for potential applications in information processing and digital storage devices. Here we report an unusual discovery of unambiguous conductance switching upon light and electric field-induced isomerisation of azobenzene in a robust single-molecule electronic device for the first time. Both experimental and theoretical data consistently demonstrate that the azobenzene sidegroup serves as a viable chemical gate controlled by electric field, which efficiently modulates the energy difference of trans and cis forms as well as the energy barrier of isomerisation. In conjunction with photoinduced switching at low biases, these results afford a chemically-gateable, fully-reversible, two-mode, single-molecule transistor, offering a fresh perspective for creating future multifunctional single-molecule optoelectronic devices in a practical way.

The construction of three-dimensional covalent organic frameworks (3D COFs) has proven to be very challenging, as their synthetic driving force mainly comes from the formation of covalent bonds. To facilitate the synthesis, rigid building blocks are always the first choice for designing 3D COFs. In principle, it should be very appealing to construct 3D COFs from flexible building blocks, but there are some obstacles blocking the development of such systems, especially for the designed synthesis and structure determination. Herein, we reported a novel highly crystalline 3D COF (FCOF-5) with flexible C–O single bonds in the building block backbone. By merging 17 continuous rotation electron diffraction data sets, we successfully determined the crystal structure of FCOF-5 to be a 6-fold interpenetrated pts topology. Interestingly, FCOF-5 is flexible and can undergo reversible expansion/contraction upon vapor adsorption/desorption, indicating a breathing motion. Moreover, a smart soft polymer composite film with FCOF-5 was fabricated, which can show a reversible vapor-triggered shape transformation. Therefore, 3D COFs constructed from flexible building blocks can exhibit interesting breathing behavior, and finally, a totally new type of soft porous crystals made of pure organic framework was announced.

Transferring the solution-state chemistry of organic-based molecular switches (OMS) into the solid state usually faces several fatal problems, such as spatial confinement or inefficient conversion. As a result, their switching behavior usually cannot be maintained. Herein, we report a redoxswitchable metal−organic framework (MOF) that can undergo a reversible single-crystal-to-single-crystal (SCSC) transformation through a hydroquinone/quinone redox reaction. The redox-triggered transformation is quantitatively reversible while maintaining the crystallinity of the MOF scaffold. In addition, the transformation occurs gradually in the MOF backbone and from the outsurface of MOF to the inside. This study represents a general strategy to enable efficient conversion of the functionality of an OMS from solution into solid state, by incorporation of OMS into the framework of MOF. Furthermore, the material exhibits interesting changes in spectroscopic properties through reversible SCSC transformation and, thus, may be a starting point for the use of such materials in memory storage or redox-based electronic devices.