Jarrod F. Eubank

In this review, we describe two recently implemented conceptual approaches facilitating the design and deliberate construction of metal–organic frameworks (MOFs), namely supermolecular building block (SBB) and supermolecular building layer (SBL) approaches. Our main objective is to offer an appropriate means to assist/aid chemists and material designers alike to rationally construct desired functional MOF materials, made-to-order MOFs. We introduce the concept of net-coded building units (net-cBUs), where precise embedded geometrical information codes uniquely and matchlessly a selected net, as a compelling route for the rational design of MOFs. This concept is based on employing pre-selected 0-periodic metal–organic polyhedra or 2-periodic metal–organic layers, SBBs or SBLs respectively, as a pathway to access the requisite net-cBUs. In this review, inspired by our success with the original rht-MOF, we extrapolated our strategy to other known MOFs via their deconstruction into more elaborate building units (namely polyhedra or layers) to (i) elucidate the unique relationship between edge-transitive polyhedra or layers and minimal edge-transitive 3-periodic nets, and (ii) illustrate the potential of the SBB and SBL approaches as a rational pathway for the design and construction of 3-periodic MOFs. Using this design strategy, we have also identified several new hypothetical MOFs which are synthetically targetable.

This review highlights various design and synthesis approaches toward the construction of ZMOFs, which are metal-organic frameworks (MOFs) with topologies and, in some cases, features akin to traditional inorganic zeolites. The interest in this unique subset of MOFs is correlated with their exceptional characteristics arising from the periodic pore systems and distinctive cage-like cavities, in conjunction with modular intra- and/or extra-framework components, which ultimately allow for tailoring of the pore size, pore shape, and/or properties towards specific applications.

The key to soc-cess: The trimer building block [In3O(CO2)6] and a tetracarboxylate organic linker assemble into a novel porous metal–organic framework (see picture; In green, C gray, N blue, O red; cavity: yellow sphere) having an unprecedented soc topology (soc=square–octahedron) and high H2 uptake. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z604306_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Here, we report a novel approach for the bottom-up assembly of hierarchical building blocks: simple molecular building blocks (MBBs) and the resultant supermolecular building blocks (SBBs) to build highly coordinated nets. A specific network, the (3,24)-connected rht, was used as a blueprint to construct a metal-organic framework where the MBBs/SBBs augment the net.