Volume 94 Issue 38 | pp. 28-29
Issue Date: September 26, 2016

The inorganic kids are alright

The Division of Inorganic Chemistry’s Young Investigator Awards program celebrates a decade of highlighting new talent
Department: Science & Technology
News Channels: Analytical SCENE, Biological SCENE, Environmental SCENE, JACS In C&EN, Materials SCENE
Keywords: ACS meeting news, awards, young investigator, inorganic chemistry

In 2005, the American Chemical Society’s Division of Inorganic Chemistry (DIC) started something new. It was a simple idea to host an annual symposium to showcase the research of some of the field’s brightest young stars. Eight DIC Young Investigators were named that year, and they gave presentations at theACS fall national meeting in Washington, D.C., an intriguing event that seemed to be heading somewhere special.

Now, just over a decade later, with the number of honorees approaching 100, the DIC leadership thought it was a good time for a Young Investigator reunion. To that end, the division hosted a “Where Are They Now?” symposium at the ACS national meeting in Philadelphia last month.

The symposium brought together 13 former Young Investigator awardees to reflect on the work they were doing when they received the honor and to describe, in a nutshell, their career path since then and their current research efforts. The division held a separate symposium in Philadelphia to honor this year’s award recipients.

“These past Young Investigator awardees are enjoying diverse careers at universities, companies, and national labs all around the world,” said John D. Protasiewicz of Case Western Reserve University, DIC’s chair-elect. Protasiewicz, along with Massachusetts Institute of Technology’s Christopher C. Cummins and Georgetown University’s Timothy H. Warren, co-organized the Philadelphia symposium. “The special reunion event is a milestone for this very successful program,” Protasiewicz said.

The DIC Young Investigator program was the brainchild of T. Don Tilley of the University of California, Berkeley, when he was division chair in 2003. “The Inorganic Division is one of the largest and most active at ACS meetings, with a strong tradition of devoting much of the program to oral and poster presentations by young people—our success has been largely due to students and postdocs,” Tilley told C&EN.

“These past Young Investigator awardees are enjoying diverse careers at universities, companies, and national labs all around the world.”

John D. Protasiewicz, DIC’s chair-elect, Case Western Reserve University

Tilley added that there was a general feeling at the time that the division could do more and come up with innovative ways to better serve its members. “We believed showcasing the best new results in inorganic chemistry in an annual symposium would bolster DIC’s national meeting programming, recognize the contributions and dedication of graduate students and postdocs, and provide a way to check out rising stars in inorganic chemistry.”

The DIC Young Investigator program was thus born. It has now been used as a model for other ACS technical divisions to create similar programs to recognize the talents of early-career researchers. It also has sparked ACS journals to create young investigator lectureship awards and other recognition for researchers based on their published work.

To be selected for the DIC award, candidates must be nominated by an adviser and they must be DIC members who are enrolled as graduate students or hold positions as postdoctoral fellows in academia, industry, or a government lab. The nominee also must be no more than one year beyond completion of their Ph.D., and awardees cannot have accepted a permanent, independent position at the time of selection.

Up to eight awards are given each year, at most two each in the Bioinorganic, Nanoscience, Organometallic, and Solid-State & Materials subdivisions. Each awardee receives a $1,000 honorarium and a plaque, plus they have the opportunity to give a 30-minute presentation in the award symposium at the ACS fall national meeting.

Theodore A. Betley, now a chemistry professor at Harvard University, was in the first class of DIC Young Investigators. During the inaugural symposium in 2005, he presented his Ph.D. research on the redox chemistry of iron that he carried out at California Institute of Technology in the lab of Jonas C. Peters.

“Iron is an interesting metal because it plays a central role in many biological and industrial processes,” Betley said during his 2005 talk. “With the right ligand platform, we can access five different oxidation states with iron through substitution of a single ligand. This redox flexibility becomes essential when describing iron’s potential role in certain chemical transformations, such as dinitrogen activation.”

These days, Betley’s group at Harvard continues to work on developing new types of iron complexes, among other things. One target is performing atom- and group-transfer catalysis, for instance, synthesizing complex N-heterocycles such as pyrrolidines via direct C–H bond amination reactions.

“The Young Investigator symposium draws a large crowd and provides an excellent opportunity for the awardees to address a cross section of the chemistry community,” Betley told C&EN. “For me, that was an exciting springboard right before applying for jobs. It gave me terrific exposure.”

Betley has had three subsequent DIC Young Investigators in his Harvard research group, and as a result, he has the distinction of being the first Young Investigator grandpa. Alison R. Fout (2010) was a postdoc in Betley’s group and now is an assistant professor at the University of Illinois, Urbana-Champaign. Ellen M. Matson (2014) was in turn a postdoc in Fout’s group at Illinois and now is an assistant professor at the University of Rochester. Both Fout and Matson were speakers in the Philadelphia reunion symposium.

“Being a Young Investigator was a tremendous honor to receive as I was finishing my Ph.D.,” noted Jillian L. Dempsey (2010), now an assistant professor at the University of North Carolina, Chapel Hill. “It really made me recognize how much my adviser’s support and enthusiasm was instrumental in my success as a scientist. As a PI, I’ve realized how important it is for me to give my own students the encouragement and support they need to realize their own goals.”

For Jinhee Park (2013), being selected a Young Investigator provided a measure of confidence to start her career, an experience shared by several of the reunion awardee speakers. In graduate school at Texas A&M University, Park was in Hong-Cai Zhou’s group developing metal-organic materials with light-activated functional groups for electronics applications.

After graduating, Park worked for two years as a senior researcher at Korea Electrotechnology Research Institute. “Thanks to the Young Investigator Award, I became confident enough in doing research to use my knowledge and experience to help small businesses that do not have sufficient facilities and technical know-how,” Park said. “It was a great opportunity to work with others to transfer the technology our group developed.” Earlier this year, she became an assistant professor at Daegu Gyeongbuk Institute of Science & Technology.

The accomplishment many DIC Young Investigators hold most dear is a memorable research paper, often the first one in which their name appears as a coauthor. Caroline T. Saouma (2012), an assistant professor at the University of Utah, attached special meaning to one of her papers, in part because it focused on a new type of hydrazido iron complex, but also because of the Herculean effort it took to acquire some of the data.

Saouma was a Caltech graduate student in Peters’s group, but spent some of her time in Boston when Peters moved to MIT. She was studying reactions of synthetic iron complexes to shed light on possible nitrogen reduction mechanisms (Angew. Chem. Int. Ed. 2011, DOI: 10.1002/anie.201006299). Saouma kept trying to grow crystals of an Fe(N2H3) species, but her compound kept changing color--her orange crystals became covered with green fernlike crystals of another species. “I was annoyed because it was some type decomposition, later attributed to trace oxygen, and I wanted to know what the product was.”

By the time Saouma had good crystals of the decomposition product and instrument time to analyze the compound, it was a Sunday, the day before she was to go home for the winter holidays. It was also the day after a blizzard hit Boston. Saouma, who is a rower, had gone to the Riverside Boat Club for a morning workout, then trekked to campus in the afternoon to mount the crystals and start the data collection before going home to dig her car out and pack.

“I came back a week later, and was glued to the computer until I was done solving and refining the crystal structure,” Saouma told C&EN. “I was so surprised by what I was seeing, I had to make sure that I didn’t let my excitement misinterpret the data.” Once she was convinced, Saouma got to work figuring out how to make the new species and solving the structural puzzle of the Fe-N2H2-Fe core, a new type of bonding for N2H2 ligands. “It was the best chemistry Christmas present ever.” 

Where are they now?

These 13 past recipients of the Division of Inorganic Chemistry Young Investigator Award spoke at the American Chemical Society national meeting in Philadelphia last month.

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Theodore Betley
Photo of Theodore Betley
 
Theodore Betley

Theodore A. Betley

Then: 2005, Caltech (Jonas C. Peters)/MIT (Daniel G. Nocera)

Now: professor, Harvard University

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This new pyrrolidine prepared by Betley’s group was formed via a direct iron-catalyzed C–H bond amination reaction. The iron group is still attached in this structure.
Credit: Ted Betley
Structure of an iron-coordinated pyrrolidine.
 
This new pyrrolidine prepared by Betley’s group was formed via a direct iron-catalyzed C–H bond amination reaction. The iron group is still attached in this structure.
Credit: Ted Betley

Research, in my own words: My graduate research involved fundamental studies to stabilize reactive intermediates along the dinitrogen reduction pathway (from N2 to N3–), which hinted at the viability of an iron-mediated N2 reduction process. The key to maximizing the stability of the then-rare high-oxidation-state iron nitride was targeting low-spin metal-ligand electronic structures. My group now tries to increase the reactivity of metal-ligand multiple bonds by maximizing their instability. We achieve this by targeting high-spin iron complexes, whose electronic configurations make the complexes ideal for performing atom- and group-transfer catalysis, for instance, synthesizing complex N-heterocycles such as the pyrrolidine shown via direct C–H bond amination reactions.

Favorite research paper: This is a bit of a cop out, but I really don’t have a favorite paper—I just get a kick out of making molecules that have no right to be isolable.

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Robin Macaluso
Photo of Robin Macaluso
 
Robin Macaluso

Robin T. Macaluso

Then: 2005, Argonne National Laboratory (John Mitchell)

Now: associate professor, University of Texas, Arlington

Research, in my own words: When I was selected as a DIC Young Investigator, I was a postdoc at Argonne National Lab. The research I was doing during that time was about the synthesis and structure-property relationships of heavy-fermion intermetallic compounds with interesting superconducting, magnetic, and optical behavior. In my current research, I carry over the idea that structure and physical behavior are intimately related, extending my work to include neutron and X-ray scattering to help explore structural details (a collage of new materials shown). As a solid-state chemist, many of my collaborators are in physics or materials science. Being selected a Young Investigator assured my identity as a chemist and that my contributions to these questions dominated by other disciplines were valued by the chemistry community.

Favorite research paper: Robin T. Macaluso, Satoru Nakatsuji, Kentaro Kuga, Evan Lyle Thomas, Yo Machida, Yoshiteru Maeno, Zachary Fisk, and Julia Y. Chan; “Crystal Structure and Physical Properties of Polymorphs of LnAlB4, Ln = Yb, Lu” (Chem. Mater. 2007, DOI: 10.1021/cm062244+)

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Liviu Mirica
Photo of Liviu Mirica
 
Liviu Mirica

Liviu M. Mirica

Then: 2006, Stanford (T. Daniel P. Stack)/ UC Berkeley (Judith P. Klinman)

Now: professor, Washington University in St. Louis

Research, in my own words: As a graduate student, I worked on the reactivity and mechanistic studies of copper complexes that were synthetic models of copper oxidase enzymes. My group’s research program currently includes projects focused on the organometallic chemistry of high-valent palladium and nickel complexes that are catalysts for cross-coupling and other reactions. In these studies we take advantage of the expertise I gained during my training years in performing complex mechanistic and spectroscopic analyses of inorganic systems, including the first isolated Ni(III)-dialkyl species shown. Such species have been widely proposed to be active intermediates in nickel-catalyzed cross-coupling reactions.

Favorite research paper: Jason W. Schultz, Kei Fuchigami, Bo Zheng, Nigam P. Rath, and Liviu M. Mirica; Isolated Organometallic Nickel(III) and Nickel(IV) Complexes Relevant to Carbon-Carbon Bond Formation Reactions (J. Am. Chem. Soc. 2016, DOI: 10.1021/jacs.6b06862).

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Amanda Reig
Photo of Amanda Reig
 
Amanda Reig

Amanda Reig

Then: 2007 University of Wisconsin, Madison (Thomas C. Brunold)/University of Pennsylvania (William F. DeGrado)

Now: associate professor, Ursinus College

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Young Investigator Amanda Reig of Ursinus College and her group prepared this de novo designed diiron metalloprotein, 3His-G4DFsc, which catalyzes the four-electron oxidation of p-anisidine.
Credit: Amanda Reig
Ribbon structure of an enzyme.
 
Young Investigator Amanda Reig of Ursinus College and her group prepared this de novo designed diiron metalloprotein, 3His-G4DFsc, which catalyzes the four-electron oxidation of p-anisidine.
Credit: Amanda Reig

Research, in my own words: In graduate school, I used a combination of spectroscopic and computational techniques to generate an experimentally validated electronic structure of coenzyme B12. These studies then allowed us to explore how the electronic structure of the B12 cofactor is modulated by isomerase enzymes to promote homolytic cleavage of the cofactor’s strong Co–C bond and initiate radical-based substrate rearrangement reactions. I now design and characterize functional de novo protein models for binuclear metalloenzymes, and use many of the same techniques in collaboration with the Solomon Lab at Stanford University to gain molecular-level mechanistic insights into their reactivity. The de novo designed diiron metalloprotein 3His-G4DFsc, which catalyzes the four-electron oxidation of p-anisidine, is shown.

Favorite research paper: Troy A. Stich, Amanda J. Brooks, Nicole R. Buan, and Thomas C. Brunold; Spectroscopic and Computational Studies of Co3+-Corrinoids: Spectral and Electronic Properties of the B12 Cofactors and Biologically Relevant Precursors” (J. Am. Chem. Soc. 2003, DOI: 10.1021/ja029328d)

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Joel Rosenthal
Photo of Joel Rosenthal
 
Joel Rosenthal

Joel Rosenthal

Then: 2007, MIT (Daniel G. Nocera)

Now: associate professor, University of Delaware

Research, in my own words: My Ph.D. thesis project focused on the mechanistic pathways by which proton and electron motion can be coupled to one another, which we applied to designing catalysts capable of driving interconversion of O2 and H2O for energy applications. In my research group at Delaware, we are applying similar strategies to those that I helped develop in the Nocera lab to build inexpensive architectures that take advantage of proton-coupled electron transfer to drive uphill energy-storing transformations, such as the reduction of carbon dioxide to fuels and other value-added compounds. My group is building on those concepts to also develop emissive microelectrode arrays that can detect interactions between biomolecules and potential drug molecules via electrochemiluminescence.

Favorite research paper: John L. DiMeglio and Joel Rosenthal; “Selective Conversion of CO2 to CO with High Efficiency Using an Inexpensive Bismuth-Based Electrocatalyst” (J. Am. Chem. Soc. 2013, DOI: 10.1021/ja4033549).

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Michael Pluth
Photo of Michael  Pluth
 
Michael Pluth

Michael D. Pluth

Then: 2008, UC Berkeley (Robert G. Bergman and Kenneth N. Raymond)

Now: assistant professor, University of Oregon

Research, in my own words: In 2008, my graduate work on supramolecular catalysis focused on carrying out reactions in the interior cavity of self-assembled “molecular flasks.” My lab is now working on developing new chemical tools for investigating the multifaceted roles of biological hydrogen sulfide, H2S. One theme that has joined my graduate, postdoctoral, and current work is molecular recognition—namely, designing structures with specific recognition motifs and investigating the mechanisms by which small molecules exert their action in complex environments.

Favorite research paper: Andrea K. Steiger, Sibile Pardue, Christopher G. Kevil, and Michael D. Pluth; “Self-Immolative Thiocarbamates Provide Access to Triggered H2S Donors and Analyte Replacement Fluorescent Probes” (J. Am. Chem. Soc. 2016, DOI: 10.1021/jacs.6b03780)

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Brandi Cossairt
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Brandi Cossairt

Brandi M. Cossairt

Then: 2009, MIT (Christopher C. Cummins)

Now: assistant professor, University of Washington

Research, in my own words: In my research at MIT I was trying to develop new ways to transform white phosphorus (P4) into novel and useful phosphorus-containing compounds. A notable example was AsP3, a tetratomic molecule very similar to P4, but that had never previously been isolated and put into a bottle. Today, my chemistry is still focused on building complex clusters and materials with atom-level precision. One of our main targets has been generating uniform samples of indium phosphide quantum dots for color displays and solid-state lighting. We recently unveiled that InP grows via a two-step nucleation mechanism with the formation of a magic-size cluster intermediate, In37P20(O2CCH2C6H5)51 (shown).

Favorite research paper: Dylan C. Gary, Sarah E. Flowers, Werner Kaminsky, Alessio Petrone, Xiaosong Li, and Brandi M. Cossairt; “Single-Crystal and Electronic Structure of a 1.3 nm Indium Phosphide Nanocluster” (J. Am. Chem. Soc. 2016, DOI: 10.1021/jacs.5b13214)

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Jillian Dempsey
Credit: Photo of Jillian Dempsey
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Jillian Dempsey
Credit: Photo of Jillian Dempsey

Jillian L. Dempsey

Then: 2010, Caltech (Harry B. Gray and Jay R. Winkler)/University of Washington (Daniel R. Gamelin)

Now: assistant professor, University of North Carolina, Chapel Hill

Research, in my own words: As a graduate student, I was employing photochemical methods to track the reactivity of catalytic intermediates in cobaloxime-catalyzed hydrogen evolution. Now that I’ve started my own lab, I’m still interested in the fundamental proton-coupled electron transfer reactivity underpinning solar energy conversion to produce fuels, such as hydrogen. My lab complements the time-resolved spectroscopic methods I learned as a student with electrochemical approaches to tease out reaction mechanisms and kinetics. We’ve also branched out to examine nanoscale material surface chemistry and look at other electron-transfer processes relevant to solar energy conversion, such as controlling the extent of ligand exchange reactions of oleate-capped CdSe nanocrystals (shown).

Favorite research paper: Eric S. Rountree and Jillian L. Dempsey; “Potential-Dependent Electrocatalytic Pathways: Controlling Reactivity with pKa for Mechanistic Investigation of a Nickel-Based Hydrogen Evolution Catalyst” (J. Am. Chem. Soc. 2014, DOI: 10.1021/jacs.5b08297)

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Alison Fout
Photo of Alison Fout
 
Alison Fout

Alison R. Fout

Then: 2010, Indiana University (Daniel J. Mindiola)/Harvard University (Theodore A. Betley)

Now: assistant professor, University of Illinois, Urbana-Champaign

Research, in my own words: When I was selected as an awardee, I was investigating the reactivity of a transient titanium alkylidyne complex toward the ring-opening of pyridine and picolines and subsequent extrusion of the nitrogen from these N-heterocycles to form substituted arenes in a cyclic manner. My current research in synthetic inorganic chemistry is a direct reflection of what I learned as a student and postdoc. My group is designing and synthesizing base metal complexes for a variety of transformations, including oxyanion reduction and alkene/alkyne hydrogenation, and to create high-valent nickel complexes, such as the one shown.

Favorite research paper: Ellen M. Matson, Jeffrey A. Bertke, and Alison R. Fout; “Isolation of Iron(II) Aqua and Hydroxyl Complexes Featuring a Tripodal H-bond Donor and Acceptor Ligand” (Inorg. Chem. 2014, DOI: 10.1021/ic500102c)

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Yogesh Surendranath
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Yogesh Surendranath

Yogesh Surendranath

Then: 2011, MIT (Daniel G. Nocera)/UC Berkeley (A. Paul Alivisatos)

Now: assistant professor, MIT

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Young Investigator Yogesh Surendranath’s research group at MIT is developing thin-film catalysts, such as the one shown. The chemists want to understand the films’ mechanisms for reducing carbon dioxide and for other reactions important to renewable energy storage and chemical production.
Credit: Yogesh Surendranath
Reaction scheme shows a thin-film rhenium catalyst reducing CO2 to CO.
 
Young Investigator Yogesh Surendranath’s research group at MIT is developing thin-film catalysts, such as the one shown. The chemists want to understand the films’ mechanisms for reducing carbon dioxide and for other reactions important to renewable energy storage and chemical production.
Credit: Yogesh Surendranath

Research, in my own words: My graduate work focused on understanding the mechanisms of water oxidation, a key reaction for making renewable fuels from solar energy, when catalyzed by cobalt oxide-based thin films. This catalyst was unique in that it displays properties both of small molecules and extended solids. Working with these materials taught us that there’s a great deal to be learned in bridging the traditionally disparate disciplines of molecular and heterogeneous catalysis. That remains a central theme of my research group. In particular, we use electricity to rearrange chemical bonds by controlling interfacial reactivity at the molecular level. In so doing, we aim to address key global challenges in renewable energy storage and catalysis for chemical production.

Favorite research paper: Yogesh Surendranath, Matthew W. Kanan, and Daniel G. Nocera; “Mechanistic Studies of the Oxygen Evolution Reaction by a Cobalt-Phosphate Catalyst at Neutral pH” (J. Am. Chem. Soc. 2010, DOI: 10.1021/ja106102b)

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Caroline Saouma
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Caroline Saouma

Caroline T. Saouma

Then: 2012, University of Washington (James M. Mayer)

Now: assistant professor, University of Utah

Research, in my own words: When I was selected as a Young Investigator, my chemistry focused on proton-coupled electron transfer (PCET) reactions of synthetic [Fe-S] clusters, which are electron-transfer cofactors necessary for the functioning of many proteins. I was interested in establishing and understanding the feasibility of these clusters to undergo PCET, to compare the two reactivity types, and perhaps expand our mechanistic hypotheses of certain enzymatic transformations. Today, I am interested in understanding how to efficiently and selectively transfer proton and electron equivalents—essentially PCET—from synthetic clusters within metal-organic frameworks (MOFs) to small molecules, to facilitate redox reactions pertinent to the solar-energy-production landscape.

Favorite research paper: Caroline T. Saouma, R. Adam Kinney, Brian M. Hoffman, Jonas C. Peters; “Transformation of an [Fe(η2-N2H3)]+ Species to π-Delocalized [Fe2(μ-N2H2)]2+/+ Complexes” (Angew. Chem. Int. Ed. 2011, DOI: 10.1002/anie.201006299)

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Jinhee Park
Credit: Photo of Jinhee Park
09438-scitech1-park
 
Jinhee Park
Credit: Photo of Jinhee Park

Jinhee Park

Then: 2013, Texas A&M University (Hong-Cai Zhou)

Now: assistant professor, Daegu Gyeongbuk Institute of Science & Technology

Research, in my own words: The designability and intrinsic porosity of metal-organic polyhedra (MOPs) and metal-organic frameworks (MOFs) present an opportunity for developing new types of stimuli-responsive materials. As a student, our group created MOPs and MOFs functionalized with optically active moieties controlled by light irradiation, such as the azobenzene-functionalized copper-based cuboctahedral cage shown. As an extension of this work, my current research focuses on photoinduced catalytic activities of MOPs and MOFs. In between, thanks to the Young Investigator Award, I became confident enough to use my experience to assist small businesses that do not have sufficient facilities or technical know-how, while I was a senior researcher at Korea Electrotechnology Research Institute.

Favorite research paper: Jinhee Park, Lin-Bing Sun, Ying-Pin Chen, Zachary Perry, and Hong-Cai Zhou; “Azobenzene-Functionalized Metal–Organic Polyhedra for the Optically Responsive Capture and Release of Guest Molecules” (Angew. Chem. Int. Ed. 2014, DOI: 10.1002/anie.201310211)

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Ellen Matson
Photo of Ellen Matson
 
Ellen Matson

Ellen M. Matson

Then: 2014, Purdue University (Suzanne C. Bart)/University of Illinois, Urbana-Champaign (Alison R. Fout)

Now: assistant professor, University of Rochester

Research, in my own words: When I was named a Young Investigator, I had just finished my Ph.D. on the synthesis, characterization, and reactivity of uranium(III) alkyl complexes. My postdoc provided me with a complementary experience, with work on the design of a ligand featuring a redox noninnocent framework and a secondary coordination sphere. Those projects focused on inorganic synthesis as a tool to design molecules that can replace precious metals in important transformations. My research group is now using synthesis to generate a family of heterometallic clusters based on mixed-valent polyoxovanadate alkoxides (one shown). These systems possess remarkably rich redox chemistry, and we are looking forward to probing their reactivity. Stay tuned

Favorite research paper: Feng Li, Lauren E. VanGelder, William W. Brennessel, and Ellen M. Matson; “Self-Assembled, Iron-Functionalized Polyoxovanadate Alkoxide Clusters” (Inorg. Chem. 2016, DOI: 10.1021/acs.inorgchem.6b01349).

 
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