个人简介

Dr. Cozzolino hails from Ontario Canada where he completed his graduate work at McMaster University under the supervision of Prof. Ignacio Vargas-Baca. There he designed new supramolecular materials that self-assemble through tellurium-nitrogen interactions. Following this, he worked as an NSERC postdoctoral fellow at MIT with Prof. Christopher Cummins where he learned how to make and characterize some extremely reactive paramagnetic coordination complexes. He then joined Prof. Mircea Dinca’s group at MIT as a postdoctoral associate in order to help take metal-organic frameworks in some unique directions. Dr. Cozzolino accepted a position as an Assistant Professor at Texas Tech University in 2013 and is pursuing new molecular and supramolecular materials.

研究领域

Inorganic and Supramolecular Materials Chemistry

Inorganic Synthesis (Supra)molecular Materials Smart Molecules I am interested in research challenges related to current problems of technological and environmental significance. Central to my effort is the concept of engineered complexity where modern computational methods are used to guide the combination of well defined components into functional smart molecules and materials. My research program has three major objectives: A) use light to enhance the reactivity of transition-metal complexes through photoswitchable ligands, B) use molecular recognition to drive the self-assembly of molecular electronics, and C) achieve conductivity in porous materials mediated by the efficient electronic overlap between p-block elements and organic bridges. A) Redox-active unsaturated early transition metal complexes are capable of activating small molecule substrates. The resulting species are often thermodynamically stable products. We will be using photoswitchable ligands to modulate the redox properties of coordination complexes. These smart molecules will be used to drive the transformation of ubiquitous small molecules like CO2 into value-added products. B) Secondary bonding interactions (SBIs) are structure directing attractive interactions involving heavy p-block atoms. We will prepare a series of supramolecular pairs that selectively self-assemble through SBIs. These sets of molecules will be the inorganic equivalent to DNA base pairs. We will use these pairs to direct the self-assembly of supramolecular diodes and wires, providing a method – supramolecular synthesis – for preparing integrated molecular electronics. C) A conductive porous framework would have many applications. MOFs, a promising class of materials, are most often characterized by coordination bonds between hard anions and hard cations. The result is poor orbital overlap causing the electrons to be ‘trapped’ at the metal nodes. We will utilize the more favorable energetic overlap between p-block elements in the design of network solids by using p-block clusters as nodes in frameworks. These frameworks will be considered for applications such as electrodes for batteries, fuel cells, capacitors, sensors and molecular wires. Opportunities to Acquire Expertise Students in my group will acquire a broad spectrum of practical skills including inorganic synthesis (using p-block and d-block elements), organic synthesis (through ligand design), structure determination through spectroscopic and diffraction techniques, and modern computational methods. As your project progresses you will have ample opportunity to learn and apply specialized techniques either independently or through collaborative efforts.

近期论文

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Cozzolino, A. F.; Brozek, C. K.; Palmer, R. D.; Yano, J.; Li, M.; Dinca, M. Ligand Redox Non-Innocence in the Stoichiometric Oxidation of Mn 2 (2,5-Dioxidoterephthalate) (Mn-MOF-74). J. Am. Chem. Soc. 2014, 136, 3334–3337. Cozzolino, A. F.; Silvia, J. S.; Lopez, N.; Cummins, C. C. Experimental and computational studies on the formation of cyanate from early metal terminal nitrido ligands and carbon monoxide. Dalton Trans. 2014, 43, 4639–4652. Shustova, N. B.; Cozzolino, A. F.; Reineke, S.; Baldo, M.; Dincă, M. Selective Turn-on Ammonia Sensing Enabled by High-Temperature Fluorescence in Metal-Organic Frameworks with Open Metal Sites. J. Am. Chem. Soc. 2013, 135, 13326–13329. Brozek, C. K.; Cozzolino, A. F.; Teat, S. J.; Chen, Y.-S.; Dinca, M. Quantification of Site-Specific Cation Exchange in Metal-Organic Frameworks using Multi-Wavelength Anomalous X-ray Dispersion. Chem. Mater. 2013, 10.1021/cm400858d. Palluccio, T. D.; Rybak-Akimova, E. V; Majumdar, S.; Cai, X.; Chui, M.; Temprado, M.; Silvia, J. S.; Cozzolino, A. F.; Tofan, D.; Cummins, C. C.; Captain, B.; Hoff, C. D.; Velian, A. Thermodynamic and Kinetic Study of Cleavage of the N-O Bond of N-oxides by a Vanadium(III) Complex: Enhanced Oxygen Atom Transfer Reaction Rates for Adducts of Nitrous Oxide and Mesityl Nitrile Oxide. J. Am. Chem. Soc. 2013, 10.1021/ja405395z. Cozzolino, A. F.; Elder, P. J. W.; Lee, L. M.; Vargas-Baca, I. The Role of the Lewis Acid−base Properties in the Supramolecular Association of 1,2,5-Chalcogenadiazoles. Can. J. Chem. 2013, 91, 338–347. Cozzolino, A. F.; Dimopoulos-Italiano, G.; Lee, L. M.; Vargas-Baca, I. Chalcogen-Nitrogen Secondary Bonding Interactions in the Gas Phase - Spectrometric Detection of Ionized Benzo-2,1,3-telluradiazole Dimers. Eur. J. Inorg. Chem. 2013, 2013, 2751–2756. Shustova, N. B.; Ong, T.-C.; Cozzolino, A. F.; Michaelis, V. K.; Griffin, R. G.; Dincă, M. Phenyl Ring Dynamics in a Tetraphenylethylene-bridged Metal-organic Framework: Implications for the Mechanism of Aggregation-induced Emission. J. Am. Chem. Soc. 2012, 134, 15061–15070. Cozzolino, A. F.; Tofan, D.; Cummins, C. C.; Temprado, M.; Palluccio, T. D.; Rybak-Akimova, E. V.; Majumdar, S.; Cai, X.; Captain, B.; Hoff, C. D. Two-step Binding of O2 to a Vanadium(III) Trisanilide Complex to form a Non-vanadyl Vanadium(V) Peroxo Complex. J. Am. Chem. Soc. 2012, 134, 18249–18252. Elder, P. J. W.; Landry, J. C.; Cozzolino, A. F.; Chapman, A. E. A.; Vargas-Baca, I. A Push–pull Azobenzene is Mercurated Twice at the Ring with Less Electron Density. J. Organomet. Chem. 2012, 716, 11–18. Shustova, N. B.; Cozzolino, A. F.; Dincă, M. Conformational Locking by Design: Relating Strain Energy with Luminescence and Stability in Rigid Metal-organic Frameworks. J. Am. Chem. Soc. 2012, 134, 19596–9. Curley, J. J.; Cozzolino, A. F.; Cummins, C. C. Nitrogen Fixation to Cyanide at a Molybdenum Center. Dalton Trans. 2011, 40, 2429–32. Cozzolino, A. F.; Elder, P. J. W.; Vargas-Baca, I. A Survey of Tellurium-centered Secondary-bonding Supramolecular Synthons. Coord. Chem. Rev. 2011, 255, 1426–1438. Cozzolino, A. F.; Vargas-Baca, I. Parametrization of a Force Field for Te−N Secondary Bonding Interactions and Its Application in the Design of Supramolecular Structures Based on Heterocyclic Building Blocks. Cryst. Growth Des. 2011, 11, 668–677. Moroz, Y. S.; Cozzolino, A. F.; Rybak-Akimova, E. V; Cummins, C. C. Bis(μ2-η2:η2-2,4,6-trimethyl-benzonitrile)-bis-[(N-isopropyl-3,5-dimethyl-anilido)molybdenum(III)](Mo-Mo). Acta Crystallogr., Sect. E 2011, 67, m1643–m1644. Cozzolino, A. F.; Yang, Q.; Vargas-Baca, I. Engineering Second-Order Nonlinear Optical Activity by Means of a Noncentrosymmetric Distortion of the [Te−N]2 Supramolecular Synthon. Cryst. Growth Des. 2010, 10, 4959–4964. Cozzolino, A. F.; Whitfield, P. S.; Vargas-Baca, I. Supramolecular Chromotropism of the Crystalline Phases of 4,5,6,7-Tetrafluorobenzo-2,1,3-telluradiazole. J. Am. Chem. Soc. 2010, 132, 17265–17270. Lee, L. M.; Elder, P. J. W.; Cozzolino, A. F.; Yang, Q.; Vargas-Baca, I. An Experimental and Computational Investigation of the Formation and Structures of N-Hydro- and N,N’-Dihydro-benzo-2,1,3-chalcogenadiazolium Chlorides. Main Group Chem. 2010, 9, 117–133. Cozzolino, A. F.; Bain, A. D.; Hanhan, S.; Vargas-Baca, I. N-Triphenylboryl- and N,N’-Bis(triphenylboryl)benzo-2,1,3-telluradiazole. Chem. Commun. 2009, 8, 4043–4045. Ogini, F. O.; Ortin, Y.; Mahmoudkhani, A. H.; Cozzolino, A. F.; McGlinchey, M. J.; Vargas-Baca, I. An Investigation of the Formation of 1,3,5-Heterosubstituted Benzene Rings by Cyclo-condensation of Acetyl-substituted Organometallic Complexes. J. Organomet. Chem. 2008, 693, 1957–1967.