Figuring out the rules: We are interested in discovering and developing new ways in which simple building blocks may be induced to self-assemble into complex structures. Our investigations currently focus upon the self-assembly of imine bonds around metal-ion templates, bringing both covalent C=N and coordinative N→Metal bonds into being during the same overall self-assembly process. The structures thus created can rearrange in well-defined ways at both covalent and coordinative linkages. Ongoing projects include:
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Container Molecules. The diamine and aldehyde shown above self-assemble with iron(II) in water to form a tetrahedral cage. This cage traps guest molecules within its cavity with high selectivity. The cage may be opened and the guest released using different triggers, one of which is a drop in pH. Applications in drug delivery are of interest, as are investigations of changes in the reactivity and behaviour of guest molecules upon encapsulation. |
Functional Materials. We have recently developed means to create metal-containing conjugated polymers through self-assembly. DFT calculations carried out by Laura Gagliardi and Christopher Cramer suggest that these might conduct electricity. Studies are thus being undertaken to investigate their properties. |
Protein-Like Objects. In collaboration with the groups of Ivan Huc and Sijbren Otto, we are examining the use of a dynamic self-assembly methodology to link foldamers together into protein- sized assemblies having well-defined tertiary structures. The functions of these objects may range from molecular recognition and catalysis to dynamic motion, as with their biological counterparts. |
Feature Article: “Metal-organic container molecules through subcomponent self-assembly”, T.K. Ronson, S. Zarra, S.P. Black, J.R. Nitschke, Chem. Commun. 2013, 49, 2476-2490.
“Enantiopure Water-Soluble Fe4L6 Cages: Host-Guest Chemistry and Catalytic Activity”, Jeanne L. Bolliger, Ana M. Belenguer, and Jonathan R. Nitschke, Angew. Chem. Int. Ed. 2013, 52, 7958-7962.
“Aqueous Self-assembly of an Electroluminescent Double-helical Metallo-polymer”, X. de Hatten, D. Asil, R.H. Friend, J.R. Nitschke, J. Am. Chem. Soc. 2012, 135, 19170-19178.
“Anion-induced Reconstitution of a Self-assembling System to Express a Chloride-binding Co10L15 Pentagonal Prism”, I.A. Riddell, M.M.J. Smulders, J.K. Clegg, Y.R. Hristova, B. Breiner, J.D. Thoburn, J.R. Nitschke, Nature Chem. 2012, 51, 751-756.
“White phosphorus is air-stable within a self-assembled tetrahedral capsule” P. Mal, B. Breiner, K. Rissanen and J.R. Nitschke, Science 2009, 324, 1697-1699.
“Systems chemistry: Molecular networks come of age” J.R. Nitschke, Nature 2009, 462, 736-738.