研究领域
Materials chemistry
Molecular framework materials
X-ray diffraction
Nanoporosity
Electronic and magnetic properties of solids
Phase transitions (structural, electronic and magnetic)
Coordination Framework Materials: Coordination frameworks are crystalline solids that contain extended networks constructed by the linkage of metal atoms by multiply-coordinating polydentate ligands. A rapid growth in the study of these materials has arisen from the realisation that metal-organic framework synthesis offers considerable flexibility and control over structure and properties, thereby offering rare pathways to rational materials design. This flexibility originates from the enormous structural and chemical diversities afforded by molecular systems, features that are less prevalent in many other branches of materials chemistry.
The recent emergence of nanoporosity in molecular frameworks has led to widespread speculation that such materials may be ideally suited for applications such as molecular separation, sensing and heterogeneous catalysis. Our primary research efforts are being directed towards exploring these issues, addressing, in particular, whether there are any limitations to this porosity and to what extent the frameworks may be thought of as rigid. Experimentation involves the synthesis of new materials by diffusion-controlled and solvothermal methods, and structural and physical characterisations using techniques that include single crystal and powder X-ray diffraction, vibrational spectroscopy (IR and Raman), TGA/DSC of guest desorption and sorption, NMR, SQUID magnetometry, EPR and theoretical modelling of guest molecule docking and packing.
Chiral Phases: The search for chiral nanoporous materials, widely regarded as a Holy Grail within solid state chemistry, is driven by the potential application of such materials for chiral separations and enantioselective syntheses. We have recently made significant in-roads into this area by developing a large and diverse array of porous, chiral molecular framework solids, including some that are the only such materials known that can be synthesised homochirally. Experiments show that these materials display a high degree of selectivity to molecular guest-exchange, as well as retaining structural framework integrity with guest removal. Investigations into the direct application of these phases for enantioseparation are underway, with an aim towards designing systems for the separation of small drug-precursor molecules
In-situ Structural Investigations: We have recently performed unique in-situ single crystal X-ray diffraction experiments of guest desorption and sorption to demonstrate the nanoporosity of specific molecular framework materials. These studies are noteworthy in providing the first quantitative proof that desolvated phases of both co-ordination and hydrogen-bonded framework lattices may be robust enough to support large regions of complete void, thereby drawing a direct link with more conventional nanoporous materials such as zeolites. Such studies are being combined with in-situ techniques such as DSC/TGA, vibrational spectroscopy, NMR and molecular modelling to generate an overall picture that combines structural information with an understanding of the selectivity, dynamics and energetics of guest-exchange.
Electronic and Magnetic Properties: The incorporation of atomic or molecular constituents with electronic or magnetic function (e.g., localised electrons, delocalised pI-systems, redox-active species, etc.) into molecular frameworks is being investigated with an aim towards constructing materials with novel electronic and magnetic properties. The vast control over structure and chemical functionality that is afforded by this molecular approach allows the property-directed design and synthesis of new magnetic and electronic materials, including, importantly, the possible combination of these properties with nanoporosity.
Hydrogen Storage: The safe and efficient storage of hydrogen gas represents one of the central challenges on the road to the proposed Hydrogen Economy. Nanoporous coordination framework materials have recently been shown to sorb large volumes of hydrogen gas at low temperature and high pressure, a property that may be attributed to their very high surface areas. Two principal challenges exist to optimise the extent and conditions of loading: 1) maximisation of surface area per mass and volume, thereby maximising potential uptake, and 2) maximisation of the dihydrogen physisorption interaction energy, thereby favouring loading at higher temperatures and lower pressures. Our investigations in this area have uncovered very high hydrogen uptakes in Prussian Blue materials and a range of highly porous metal-organic frameworks.
Negatve Thermal Expansion: We have recently discovered that a broad family of coordination frameworks undergo negative thermal expansion (NTE, ie. contraction upon warming) over broad temperature ranges. We attribute this highly unusual and potentially useful property to the existence of low energy transverse vibrations of molecular bridges within the open framework structures, the amplitude of which increase with increasing temperature. Through tuning the energy of these vibrational modes we have achieved both unprecedented NTE and approximate zero thermal expansion (ZTE) behaviour.
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Miller, R., Southon, P., Kepert, C., Brooker, S. (2016). Commensurate CO2 capture, and shape selectivity for HCCH over H2CCH2, in zigzag channels of a robust CuI(CN)(L) metal-organic framework. Inorganic Chemistry, 55(12), 6195-6200. [More Information]
Duyker, S., Peterson, V., Kearley, G., Studer, A., Kepert, C. (2016). Extreme compressibility in LnFe(CN)6 coordination framework materials via molecular gears and torsion springs. Nature Chemistry, 8(3), 270-275. [More Information]
Klein, Y., Sciortino, N., Housecroft, C., Kepert, C., Neville, S. (2016). Structure and magnetic properties of the spin crossover linear trinuclear complex [Fe3(furtrz)6(ptol)2(MeOH)4]•4(ptol)•4(MeOH) (furtrz: furanylidene-4H-1,2,4-triazol-4-amine ptol: p-tolylsulfonate). Magnetochemistry, 2(1), 1-8. [More Information]
Lennartson, A., Southon, P., Sciortino, N., Kepert, C., Frandsen, C., Morup, S., Piligkos, S., McKenzie, C. (2015). Reversible guest binding in a non-porous Fe(II) coordination polymer host toggles spin crossover. Chemistry - A European Journal, 21(45), 16066-16072. [More Information]
Nafradi, B., Choucair, M., Southon, P., Kepert, C., Forro, L. (2015). Strong interplay between the electron spin lifetime in chemically synthesized graphene multilayers and surface-bound oxygen. Chemistry: A European Journal, 21(2), 770-777. [More Information]
Murphy, M., Hua, C., Price, J., D'Alessandro, D., Kepert, C. (2015). Structures, electrochemical and spectral properties of a series of [MnN(CN)3(diimine)]- complexes. European Journal of Inorganic Chemistry, 2015 (16), 2752-2757. [More Information]
Rizzuto, F., Hua, C., Chan, B., Faust, T., Rawal, A., Leong, C., Hook, J., Kepert, C., D'Alessandro, D. (2015). The electronic, optical and magnetic consequences of delocalization in multifunctional donor-acceptor organic polymers. Physical Chemistry Chemical Physics, 17(17), 11252-11259. [More Information]
Sciortino, N., Neville, S., Desplanches, C., Letard, J., Martinez, V., Real, J., Moubaraki, B., Murray, K., Kepert, C. (2014). An investigation of photo- and pressure-induced effects in a pair of isostructural two-dimensional spin-crossover framework materials. Chemistry: A European Journal, 20(24), 7448-7457. [More Information]
Rizzuto, F., Faust, T., Chan, B., Hua, C., D'Alessandro, D., Kepert, C. (2014). Experimental and computational studies of a multi-electron donor-acceptor ligand containing the thiazolo[5,4-d]thiazole core and its incorporation into a metal-organic framework. Chemistry: A European Journal, 20(52), 17597-17605. [More Information]
Yuan, A., Zhou, H., Diao, G., Southon, P., Kepert, C., Liu, L. (2014). Gas and vapor adsorption in octacyanometallate-based frameworks Mn2[M(CN)8] (M = W, Mo) with exposed Mn2+ sites. International Journal of Hydrogen Energy, 39(2), 884-889. [More Information]
Peterson, V., Southon, P., Halder, G., Price, D., Bevitt, J., Kepert, C. (2014). Guest Adsorption in the Nanoporous Metal-Organic Framework Cu3(1,3,5-Benzenetricarboxylate)2: Combined In Situ X-ray Diffraction and Vapor Sorption. Chemistry of Materials, 26(16), 4712-4723. [More Information]
Faust, T., Usov, P., D'Alessandro, D., Kepert, C. (2014). Highly unusual interpenetration isomers of electroactive nickel bis(dithiolene) coordination frameworks. Chemical Communications, 50(84), 12772-12774. [More Information]
Ogilvie, S., Duyker, S., Southon, P., Peterson, V., Kepert, C. (2014). Host-guest adsorption behavior of deuterated methane and molecular oxygen in a porous rare-earth metal-organic framework. Powder Diffraction, 29(S1), S96-S101. [More Information]
Wu, Y., Peterson, V., Luks, E., Darwish, T., Kepert, C. (2014). Interpenetration as a mechanism for negative thermal expansion in the metal-organic framework Cu3(btb)2 (MOF-14). Angewandte Chemie: International Edition, 53(20), 5175-5178. [More Information]
Murphy, M., Keene, T., Price, J., D'Alessandro, D., Kepert, C. (2014). Magnetic and electronic properties of three new hetero-bimetallic coordination frameworks [Ru2(02CR)4][Au(CN)2] (R = benzoic acid, Furan-2-carboxylate, or Thiophen-2-carboxylate). Australian Journal of Chemistry, 67(11), 1607-1611. [More Information]
Murphy, M., Usov, P., Rizzuto, F., Kepert, C., D'Alessandro, D. (2014). Magnetic, electrochemical and optical properties of a sulfate-bridged Co(II) imidazole dimer. New Journal of Chemistry, 38(12), 5856-5860. [More Information]
Keene, T., Murphy, M., Price, J., Sciortino, N., Southon, P., Kepert, C. (2014). Multifunctional MOFs through CO2 fixation: a metamagnetic kagome lattice with uniaxial zero thermal expansion and reversible guest sorption. Dalton Transactions, 43(39), 14766-14771. [More Information]
Sundberg, J., Cameron, L., Southon, P., Kepert, C., McKenzie, C. (2014). Oxygen chemisorption/desorption in a reversible single-crystal-to-single-crystal transformation. Chemical Science, 5(10), 4017-4025. [More Information]
Clements, J., Price, J., Neville, S., Kepert, C. (2014). Perturbation of Spin Crossover Behavior by Covalent Post-Synthetic Modification of a Porous Metal-Organic Framework. Angewandte Chemie: International Edition, 53(38), 10164-10168. [More Information]
Cowan, M., Miller, R., Southon, P., Price, J., Yazaydin, O., Lane, J., Kepert, C., Brooker, S. (2014). Selective Gas Adsorption in a Pair of Robust Isostructural MOFs Differing in Framework Charge and Anion Loading. Inorganic Chemistry, 53(22), 12076-12083. [More Information]
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