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研究领域

Synthetic inorganic chemistry New materials for Greenhouse Gas capture and sequestration Electron and energy transfer in purely organic and metal-organic frameworks Solution- and solid-state spectroelectrochemical methods Fundamental and applied aspects of mixed valency Our research spans the areas of inorganic chemistry, physical chemistry and materials science and focuses on the development of functional inorganic materials that exhibit novel electronic, optical and magnetic phenomena. Potential applications range from the capture of greenhouse gases to sensors, optoelectronics devices and photocatalysis. The key aspect is gaining an understanding of the fundamental relationships between the structural features of the solution- and solid-state materials and their physical properties. Carbon Dioxide Capture: The development of more efficient processes for carbon dioxide (CO2) capture is considered a key to the reduction of greenhouse gas emissions implicated in global warming. Highly porous three-dimensional solids known as metal-organic frameworks will be developed for use as CO2 capture materials and will be characterised using a range of techniques (X-ray and neutron diffraction, thermogravimetric analysis and gas sorption measurements). The ultimate goal is the development of industrially-viable materials that can be readily integrated into industrial processes. Radical MOFs and Redox-Active Materials: This project involves the design and synthesis of purely organic and metal-organic frameworks that exhibit the highly sought-after property of redox-activity (i.e. electronic conductivity). The new materials will be based on "radical" ligands and mixed-valence metal clusters of Mo, W, Ru and Os, amongst others. Solid-state electrochemical and spectroelectrochemical techniques will be developed to investigate the conductivity properties. The opportunities for advances at a fundamental and applied level are immense, with potential applications ranging from sensors to molecular electronics devices. Photo-Active Metal-Organic Frameworks: Recently, methodologies for the postsynthetic covalent functionalisation of metal-organic frameworks have opened up fascinating prospects for building complexity into the pores. This project involves the synthesis of materials as "photoswitchable molecular sieves" in which light can be used to modulate the size and polarity of the pores. Measurements on the structural and physical properties of the materials will require the development of novel techniques to probe the light-activated gas permeation properties. Mixed Valency in "Excited" Molecules: The complex interplay between electronic and magnetic interactions is ubiquitous in chemical and physical systems (e.g., solid-state superconductors, spintronics devices) and in metalloenzymes in nature. Experimental studies in which these phenomena coexist are extremely rare. This will be addressed by developing dinuclear mixed-valence complexes which incorporate a series of bridging ligands that can mediate strong ferromagnetic coupling between metal ions with unpaired electrons. The findings will have significant implications for the experimental and theoretical understanding of systems which exhibit novel magnetic and electronic phenomena.

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Das, A., D'Alessandro, D. (2016). A linear fluorescence-quenching response in an amidine-functionalised solid-state sensor for gas-phase and aqueous CO2 detection. Dalton Transactions, 45(16), 6824-6829. [More Information] Hua, C., Abrahams, B., D'Alessandro, D. (2016). Controlling interpenetration in electroactive co(II) frameworks based on the tris(4-(pyridin-4-yl)phenyl)amine ligand. Crystal Growth and Design, 16(3), 1149-1155. [More Information] Liang, W., Coghlan, C., Ragon, F., Rubio-Martinez, M., D'Alessandro, D., Babarao, R. (2016). Defect engineering of UiO-66 for CO2 and H2O uptake - a combined experimental and simulation study. Dalton Transactions, 45(11), 4496-4500. [More Information] Chen, B., Lv, Z., Hua, C., Leong, C., Tuna, F., D'Alessandro, D., Collison, D., Zuo, J. (2016). Dinuclear ruthenium complex based on a pi-extended bridging ligand with redox-active tetrathiafulvalene and 1, 10-phenanthroline units. Inorganic Chemistry, 55(9), 4606-4615. [More Information] D'Alessandro, D. (2016). Exploiting redox activity in metal-organic frameworks: concepts, trends and perspectives. Chemical Communications, 52(58), 8957-8971. [More Information] Peristyy, A., Nesterenko, P., Das, A., D'Alessandro, D., Hilder, E., Arrua, D. (2016). Flow-dependent separation selectivity for organic molecules on metal-organic frameworks containing adsorbents. Chemical Communications, 52(30), 5301-5304. [More Information] Hua, C., Baldansuren, A., Tuna, F., Collison, D., D'Alessandro, D. (2016). In situ spectroelectrochemical investigations of the redox-active tris[4-(pyridin-4-yl)phenyl]amine ligand and a Zn2+ coordination framework. Inorganic Chemistry, 55(15), 7270-7280. [More Information] Healey, K., Liang, W., Southon, P., Church, T., D'Alessandro, D. (2016). Photoresponsive spiropyran-functionalised MOF-808: postsynthetic incorporation and light dependent gas adsorption properties. Journal of Materials Chemistry A, 4(28), 10816-10819. [More Information] Hua, C., Chan, B., Rawal, A., Tuna, F., Collison, D., Hook, J., D'Alessandro, D. (2016). Redox tunable viologen-based porous organic polymers. Journal of Materials Chemistry C, 4(13), 2535-2544. [More Information] Cui, L., Geng, Y., Leong, C., Ma, Q., D'Alessandro, D., Deng, K., Zeng, Q., Zuo, J. (2016). Synthesis, properties and surface self-assembly of a pentanuclear cluster based on the new pi-conjugated TTF-triazole ligand. Scientific Reports, 6, 25544-1-25544-8. [More Information] Chevreau, H., Liang, W., Kearley, G., Duyker, S., D'Alessandro, D., Peterson, V. (2015). Concentration-dependent binding of CO₂ and CD₄ in UiO-66(Zr). The Journal of Physical Chemistry Part C, 119(13), 6980-6987. [More Information] Chen, B., Lv, Z., Leong, C., Zhao, Y., D'Alessandro, D., Zuo, J. (2015). Crystal structures, gas adsorption, and electrochemical properties of electroactive coordination polymers based on the tetrathiafulvalene-tetrabenzoate ligand. Crystal Growth and Design, 15(4), 1861-1870. [More Information] Wang, H., Wu, Y., Leong, C., D'Alessandro, D., Zuo, J. (2015). Crystal structures, magnetic properties, and electrochemical properties of coordination polymers based on the tetra(4-pyridyl)-tetrathiafulvalence ligand. Inorganic Chemistry, 54(22), 10766-10775. [More Information] Cui, L., Zhu, F., Leong, C., Ru, J., Gao, F., D'Alessandro, D., Zuo, J. (2015). Cyanide-bridged single molecule magnet based on a manganese(III) complex with TTF-fused Schiff base ligand. Science China Chemistry, 58(4), 650-657. [More Information] Kanehashi, S., Chen, G., Scholes, C., Ozcelik, B., Hua, C., Ciddor, L., Southon, P., D'Alessandro, D., Kentish, S. (2015). Enhancing gas permeability in mixed matrix membranes through tuning the nanoparticle properties. Journal of Membrane Science, 482, 49-55. [More Information] Hua, C., Turner, P., D'Alessandro, D. (2015). Facile redox state manipulation in Cu(I) frameworks by utilisation of the redox-active tris(4-(pyridin-4-yl)phenyl)amine ligand. Dalton Transactions, 44(34), 15297-15303. [More Information] Hua, C., D'Alessandro, D. (2015). Redox-state investigation in a Co(II) framework with the redox-active tris(4-(pyridin-4-yl)phenyl)amine ligand. Supramolecular Chemistry, 27(11-12), 792-797. [More Information] Liang, W., Church, T., Zheng, S., Zhou, C., Haynes, B., D'Alessandro, D. (2015). Site isolation leads to stable photocatalytic reduction of CO2 over a rhenium-based catalyst. Chemistry - A European Journal, 21(51), 18576-18579. [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] Usov, P., McDonnell-Worth, C., Zhou, F., MacFarlane, D., D'Alessandro, D. (2015). The electrochemical transformation of the zeolitic imidazolate framework ZIF-67 in aqueous electrolytes. Electrochimica Acta, 153, 433-438. [More Information]

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