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研究领域

Research in our group lies within the general realm of synthetic Inorganic and Polymer Chemistry, with particular focus given to addressing important challenges in the fields of solar energy, catalysis and chemical sensing. In addition, through our chemical explorations, we hope to gain fundamental insight into the nature of bonding and reactivity across the Period Table. Consequently, researchers in the Rivard group will be exposed to a number of advanced synthesis and characterization techniques, including quantum mechanical (DFT) methods. Donor-acceptor Stabilization of Reactive Inorganic Species: From Chemical Curiosities to the Synthesis of Advanced Materials The discovery of new compounds that exhibit unique or unusual bonding and chemical reactivity is what motivates many researchers who study Inorganic Chemistry. This research ensures the future growth of Chemistry as a discipline, and can often lead to the development of new advanced materials and technologies that benefit society as a whole. Along these lines, we have been exploring a donor-acceptor approach towards isolating a wide range of species that were either completely unknown before, or were only present as fleeting intermediates in chemical processes. One such example is GeH2, which is a key intermediate in the synthesis of semiconducting Ge metal from GeH4: We have also extended our donor-acceptor (LB-LA) protocol to include the isolation of heavy methylene and ethylene analogues, such as SiH2, SnH2, H2SiGeH2 and H2SiSnH2, in the form of stable adducts. We are currently exploring the efficient conversion of these hydrides into functional nanoparticles, including the highly desirable thermoelectric material SiGe. Functional Inorganic Polymers: From Solar Cells to Chemical Sensors Polymers are a ubiquitous and essential part of modern living, and as a result, brand-name polymers such as Nylon, Teflon, Latex and Kevlar are now entrenched in our vocabulary. However, as impressive as these materials are, their utility is largely based upon their physical properties rather than their ability to undergo chemical reactions or interact with external stimuli such as light. Functional Polymers combine the desirable physical properties inherent to polymers with the added advantage of pre-designed chemical reactivity. The field of polymer-based solar cells (or photovoltaics: creating electricity from light) has profited tremendously from the synthesis of new functional polymers bearing inorganic elements. This research domain is of profound importance in advancing/promoting new methods of cleanly harnessing energy, as Solar radiation represents a largely untapped renewable resource; for example, 1 hour of incident Solar light contains enough power to satisfy the energy needs of the entire planet for 1 year (!). We are utilizing an organometallic approach to prepare new polymers of tunable electronic and physical properties in order to maximize their ability to capture Solar radiation and convert it into useful forms of energy. A key aspect of our synthetic route is the ability to generate a library of new polymeric species from a single precursor via metallacycle transfer (or atom replacement) chemistry. Thus we are able to hone in on the most suitable materials for polymeric solar cells with unparalleled speed and efficiency. Moreover our chemical syntheses allows us to also prepare polymers with light emitting behavior (for polymer light emitting devices) and should give us materials that act as chemical sensors for various electron rich analytes such as halides Ligand Design/Coordination Chemistry: From Umbrellas to Catalysis Recently we have developed a series of bidentate ligands featuring sterically tunable, “umbrella-shaped” triarylsilyl (-SiAr3) groups. By increasing the size of the aryl groups at silicon, unprecedented levels of steric bulk should be achieved. This principle should give us access to complexes with very low coordination numbers and enhanced reactivity. We are currently exploring these ligands to access new examples of multiple bonding in involving inorganic elements, and to prepare the next generation of highly active transition metal catalysts for the activation of small molecule substrates such as N2.

近期论文

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Tapas K. Purkait, Anindya K. Swarnakar, Glenda B. De Los Reyes, Frank A. Hegmann, Eric Rivard and Jonathan G. C. Veinot, 揙ne-pot synthesis of functionalized germanium nanocrystals from a single source precursor is reported�, Nanoscale, 2015, Advanced article, DOI: 10.1039/C4NR05125D. Gang He, Benjamin D. Wiltshire, Paul Choi, Aliaksandr Savin, Shuai Sun, Arash Mohammadpour, Michael J. Ferguson, Robert McDonald, Samira Farsinezhad, Alex Brown, Karthik Shankar and Eric Rivard, 揚hosphorescence within benzotellurophenes and color tunable tellurophenes under ambient conditions�, Chem. Commun., 2015, Advanced article, DOI: 10.1039/C4CC06529H. Gang He, Olena Shynkaruk, Melanie W. Lui, and Eric Rivard, 揝mall Inorganic Rings in the 21st Century: From Fleeting Intermediates to Novel Isolable Entities�, Chemical Reviews, 2014, 114, 7815-7880. DOI: 10.1021/cr400547x. Anindya K. Swarnakar , Sean M. McDonald , Kelsey C. Deutsch , Paul Choi , Michael J. Ferguson , Robert McDonald , and Eric Rivard, 揂pplication of the Donor朅cceptor Concept to Intercept Low Oxidation State Group 14 Element Hydrides using a Wittig Reagent as a Lewis Base�, Inorganic Chemistry, 2014, 53, 8662-8671. DOI: 10.1021/ic501265k. Paul Lummis, Mohammad R. Momeni, Melanie W. Lui, Robert McDonald, Michael J. Ferguson, Mark Miskolzie, Alex Brown and Eric Rivard, 揂ccessing Zinc Monohydride Cations through Coordinative Interactions�, Angew. Chem. Int. Ed., 2014, 53, 9347-9351. DOI: 10.1002/anie.201404611. Eric Rivard, "Donor朼cceptor chemistry in the main group", Dalton Trans. 2014, 43, 8577-8586. DOI: 10.1039/C4DT00481G. Gang He, William Torres Delgado, Devon J. Schatz, Christian Merten, Arash Mohammadpour, Lorenz Mayr, Michael J. Ferguson, Robert McDonald, Alex Brown, Karthik Shankar and Eric Rivard, 揅oaxing Solid-State Phosphorescence from Tellurophenes�, Angew. Chem. Int. Ed., 2014, 53, 4587-4591. DOI: 10.1002/anie.201307373. Christopher J. Berger, Gang He, Christian Merten, Robert McDonald, Michael J. Ferguson, and Eric Rivard, 揝ynthesis and Luminescent Properties of Lewis Base-Appended Borafluorenes�, Inorganic Chemistry, 2014, 53, 1475-1486. DOI: 10.1021/ic402408t. S. M. Ibrahim Al-Rafia, Paul A. Lummis, Anindya K. Swarnakar, Kelsey C. Deutsch, Michael J. Ferguson, Robert McDonald and Eric Rivard, 揚reparation and Structures of Group 12 and 14 Element Halide朇arbene Complexes�, Australian Journal of Chemistry, 2013, 66, 1235-1245. DOI: 10.1071/CH13209. M. R. Momeni,E. Rivard and A. Brown, 揅arbene-Bound Borane and Silane Adducts: A Comprehensive DFT Study on Their Stability and Propensity for Hydride-Mediated Ring Expansion�, Organometallics, 2013, 32, 6201-6208. DOI: 10.1021/om400791r. S. M. I. Al-Rafia, M. R. Momeni, M. J. Ferguson, R. McDonald, A. Brown and E. Rivard, 揝table Complexes of Parent Digermene: an Inorganic Analogue of Ethylene�, Organometallics, 2013, DOI: 10.1021/om400361n. (invited contribution for a special issue on 揂pplications of Electrophilic Main Group Organometallic Molecules�). S. M. I. Al-Rafia, M. R. Momeni, R. McDonald, M. J. Ferguson, A. Brown, and E. Rivard, 揅ontrolled Growth of Dichlorogermanium Oligomers from Lewis Basic Hosts�, Angew. Chem. Int. Ed. (VIP Article), 2013, 52, 6390-6395. S. M. I. Al-Rafia, J. T. Goettel, P. A. Lummis, R. McDonald, M. J. Ferguson and E. Rivard, 揚reparation of a Stable Disilicon Amidinium Heterocycle and Attempted Synthesis of an Inorganic N-Heterocyclic Carbene�, J. Organomet. Chem. 2013, 739, 26-32. S. M. I. Al-Rafia, O. Shynkaruk, S. M. McDonald, S. K. Liew, M. J. Ferguson, R. McDonald, R. H. Herber and E. Rivard, 揝ynthesis and M鰏sbauer Spectroscopy of Formal Tin (II) Dichloride and Dihydride Species Supported by Lewis Acids and Bases�, Inorg. Chem. 2013, 52, 5581-5589. Gang He, Le Kang, William Torres Delgado, Olena Shynkaruk, Michael J. Ferguson, Robert McDonald, and Eric Rivard, "The Marriage of Metallacycle Transfer Chemistry with Suzuki朚iyaura Cross-Coupling To Give Main Group Element-Containing Conjugated Polymers", JACS 2013, 135, 5360-5363. Kyle J. Sabourin, Adam C. Malcolm, Robert McDonald, Michael J. Ferguson, Eric Rivard, "Metal-free dehydrogenation of amine-boranes by an N-heterocyclic carbene", Dalton Trans. 2013, 42, 4625-4632. Adam C. Malcolm, Kyle J. Sabourin, Robert McDonald, Michael J. Ferguson, Eric Rivard, "Donor-Acceptor Complexation and Dehydrogenation Chemistry of Aminoboranes", Inorg. Chem. 2012, 51, 12905-12916. S. M. Ibrahim Al-Rafia, Robert McDonald, Michael J. Ferguson, Eric Rivard, "Preparation of Stable Low-Oxidation-State Group 14 Element Amidohydrides and Hydride-Mediated Ring-Expansion Chemistry of N-Heterocyclic Carbenes", Chem. Eur. J. 2012, 18, 13810. Sean K. Liew, S. M. Ibrahim Al-Rafia, James T. Goettel, Paul A. Lummis, Sean M. McDonald, Leah J. Miedema, Michael J. Ferguson, Robert McDonald, Eric Rivard, "Expanding the Steric Coverage Offered by Bis(amidosilyl) Chelates: Isolation of Low-Coordinate N-Heterocyclic Germylene Complexes", Inorg. Chem. 2012, 51, 5471. S. M. Ibrahim Al-Rafia, Adam C. Malcolm, Robert McDonald, Michael J. Ferguson, Eric Rivard, "Efficient generation of stable adducts of Si(II) dihydride using a donor朼cceptor approach", Chem. Comm 2012, 48, 1308.

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