Coordination Polymers & MOFs
We are designing and making coordination polymers (including metal-organic frameworks or MOFs) for a variety of new applications, including adsorption of gases such as hydrogen (for clean energy) and carbon dioxide (for carbon capture), long or short range magnetic ordering, magnetic switching (for information storage and molecular sensing), and as new materials for molecular separations. We are pursuing a number of approaches to this, including:
• Incorporation of amine groups into porous MOFs in order to increase the selectivity of CO2 sorption over other gases, such as N2, or to use as sites for further reactivity after framework assembly (post-synthetic modification).
• New classes of bridging ligands in which the bridging length can be controlled by the presence or nature of e.g. group I or II metals.
Key Publications
Chem. Commun. 2009, 5579.
Coord. Chem. Rev. 2018, 365, 1.
Chem. Mater. 2018, 30, 6614.
J. Am. Chem. Soc. 2019, 141, 3828.
Angew. Chem. Int. Ed. 2020, 59, 6090.
Metallosupramolecular Chemistry
We are interested in the assembly and properties of discrete metallosupramolecular structures. Notably, we have made large (3 nm diameter) spherical supramolecules (or ‘nanoballs’) which show a wide variety of properties. For example, they can switch between two magnetic spin states, induced by change in temperature or irradiation of light. The molecular packing also creates cavities within the solid state, and thus the crystals will readily absorb solvent vapours, hydrogen, and CO2. We have also reported a remarkable catenane which shows extensive π stacking across both rings.
Key Publications
Angew. Chem. Int. Ed. 2009, 48, 2549 & 8919.
J. Am. Chem. Soc. 2009, 131, 10372.
Small Cyano Anions
Small cyano anions have shown some remarkable chemistry, including the synthesis of a large range of transition metal and/or lanthanoid clusters which act as single molecule magnets, new coordination polymers and discrete complexes showing unusual packing motifs and ligand binding modes, new hydrogen bonding solid state networks, nucleophilic addition of alcohols and amines across the nitrile groups to give new anion families, and the production of ionic liquids containing either the free anions or even metal complexes of the anions. The versatility and range of applications of these simple anions is unprecedented.
Key Publications
Coord. Chem. Rev. 2003, 246, 103.
Chem. Commun. 2011, 47, 10189.
Topology and Interpenetration
An extremely useful way to design, understand and describe crystal structures, particularly those of coordination polymers and MOFs, is to reduce complicated structures to simple infinite networks of nodes and connectors. In addition, interpenetration (entanglement) of multiple separate networks within a single structure is now commonly observed and yet still provides many new and beautiful structural patterns. We are interested in the classification and understanding of both the topology of individual networks, and the topology of interpenetration (i.e. the different ways networks can entangle).
Key Publications
Angew. Chem. Int. Ed. 1998, 37, 1460.
CrystEngComm 2001, 3, 67.
J. Am. Chem. Soc. 2003, 125, 16170 & 2011, 133, 11406.
Chem. Commun. 2012, 48, 7899.
Comp. Coord. Chem. III 2021, 2, 368.