Synthesis and Spectroscopy of Transition Metal Complexes

James McCusker

Professor

437 CEM

517-353-1081


Research webpage


Primary Research Area

Inorganic (In)

Other Area(s) of Interest

Material (Ma)

Physical (Ph)

Research

(Research Description PDF)

The McCusker Group is interested in the physical and photophysical properties of  transition  metal  complexes. Our approach relies on a confluence of synthetic chemistry, a host of physical techniques ranging from magnetism to femtosecond time-resolved spectroscopy, and high-level theory. The simultaneous examination of chemical problems on all three of these fronts places us in a unique position to explore the physical chemistry of inorganic compounds.

Ultrafast Spectroscopy of Transition Metal Complexes. Our research efforts in this area concern the short time scale photo-induced dynamics of transition metal complexes.  By “short time scale”, we refer to processes occurring between the time a photon is absorbed by a molecule and the point at which that molecule is fully relaxed in its lowest-lying excited state. Some of the questions we are addressing with this research include the following: 1) what is the general time scale for excited-state evolution in transition metal complexes? 2) what is the mechanism of this process? 3) how do the geometric and electronic structures of the compounds, the surrounding medium, and other factors couple to and/or influence this process? and 4) to what extent can we use this information to control excited-state dynamics?  Certain of these questions are very fundamental in nature, whereas others are geared toward work on solar energy conversion.  What distinguishes the group, we believe, is our ability to carry out both the synthesis and spectroscopic characterization of a wide range of inorganic molecules.  This enables us to systematically examine chemical perturbations to excited-state electronic and geometric structure, and in so doing develop a comprehensive picture of how transition metal chromophores absorb and dissipate energy.

Spin and Spin Polarization Effects on Excitedstate Dynamics. Electron spin is a fundamental property of Nature. Although many of the more common physical observables linked to spin are well documented (e.g., magnetism), the degree to which spin and spin polarization influences the chemistry of molecular systems is not as clear. We are pursuing the design and development of chemical systems that will allow us to determine whether there exists a cause-and-effect relationship between the physical  and  photophysical  properties  of molecules and their innate spin properties, and if so, to what extent can we exploit this connection in order to manipulate the chemistry of molecular systems. Much of this work centers on the study of so-called donor-acceptor assemblies wherein energy and electron transfer processes are being examined in systems containing spin-coupled paramagnetic  fragments.  Through  careful synthetic manipulation of these compounds, correlations between the observed excitedstate  reactivity  and  the  involvement  of spin-polarized electronic states of the donor and/or acceptor can be realized. Coupled to this experimental work are theoretical studies that exploit recent advances in density functional  theory.  We  believe  that  these combined efforts will forge an important link between  magnetisn  and  electron/energy transfer processes, thereby allowing us to establish a new paradigm in the emerging field of molecular spintronics.

Selected Publications

Photosensitized, Energy Transfer-mediated Organometallic Catalysis through Electronically Excited Ni(II), Eric R. Welin, Chi “Chip” Le, Daniela M. Arias-Rotondo, James K. McCusker, and David W.C. MacMillan, Science 2017, 355, 380–385.

The Photophysics of Photoredox Catalysis: A Roadmap for Catalyst Design, Daniela M. Arias-Rotondo and James K. McCusker, Chem. Soc. Rev. 2016, 45, 5803–5820 (cover article).

Spectroelectrochemical Identification of Charge-Transfer Excited States in Transition Metal-based Polypyridyl Complexes, Allison M. Brown, Catherine E. McCusker, and James K. McCusker, Dalton Transactions 2014, 43, 17635-17646.

Synthesis and Characterization of a High- Symmetry Ferrous Polypyridyl Complex: Approaching the 5T2 /3T1 Crossing Point for Fe(II), Lindsey L. Jamula, Allison M. Brown, Dong Guo, and James K. McCusker, Inorg. Chem. 2014, 53, 15-17.

Angular Momentum Conservation in Dipolar Energy Transfer, Dong Guo, Troy E. Knight, and James K. McCusker, Science 2011, 334, 1684-1687.

Femtosecond Soft X-Ray Spectroscopy of Solvated Transition Metal Complexes: Deciphering the Interplay of Electron and Structural Dynamics, Nils Huse, Hana Cho, Kiryong Hong, Tae Kyu Kim, Lindsey Jamula, Frank M.F. de Groot, James K. McCusker, and Robert W. Schoenlein, J. Phys. Chem. Lett. 2011, 2, 880-884.

Vibrational Coherence in the Excited- State Dynamics of Cr(acac)3: Probing the Reaction Coordinate for Ultrafast Intersystem Crossing, Joel N. Schrauben, Kevin L. Dillman, Warren F. Beck, and James K. McCusker, Chem. Sci. 2010, 1, 405-410.

CV

B.S. and M.S., 1987, Bucknell Univ.

Ph.D., 1992, Univ. of Illinois at Urbana Champaign

NIH Post-Doctoral Fellow, 1992-94, Univ. of North Carolina at Chapel Hill

Hellman Faculty Fellow, 1997-98, Univ. of California at Berkeley

Alfred P. Sloan Fellow, 1998-2000

Awards/Honors

2016 Outstanding Faculty Award Michigan State University (College of Natural Science)
2016 Fellow of Royal Society of Chemistry Royal Society of Chemistry
2013 CNS Junior Faculty Mentoring Award
2011 Councilor to the American Chemical Society by the Division of Inorganic Chemistry
2005 Program Committee International Conference on Bio-Inorganic Chemistry
2004 Awards Committee Inter-American Photochemical Society
2003 Organizer American Chemical Society (National Meeting - From Mixed-Valency to Single-Molecule Magnets: A Symposium in Honor of the Work of David N. Hendrickson)
2003 NSF Career Award panelist (Inorganic, Bioinorganic, and Organometallic Chemistry subdivision) National Science Foundation
2003 Organizing Committee Member 14th Inter-American Photochemical Society Winter Meeting
2002 - 2003 Nominations and Symposia Planning Committee, Division of Inorganic Chemistry American Chemical Society
1999 Department of Chemistry Teaching Award University of California, Berkeley
1998 - 2000 Alfred P. Sloan Fellowship Alfred P. Sloan Foundation
1997 - 1998 Hellman Fellow University of California, Berkeley
1992 - 1994 Postdoctoral Fellow National Institutes of Health
1992 Ph.D. University of Illinois, Urbana-Champaign
1992 - 1994 Postdoctoral Fellow National Institutes of Health
1987 M.S. Bucknell University
1987 Bachelor of Science Bucknell University
1987 cum laude Bucknell University
1987 - 1988 Graduate Fellowship University of Illinois, Urbana-Champaign
1987 Outstanding Senior Chemistry Major of the Year American Chemical Society ((Susquehanna Valley Section) and the Faculty of Bucknell University)
1987 Honorable Mention National Science Foundation Graduate Fellowship Competition
1987 Phi Beta Kappa Phi Beta Kappa
1985 Phi Eta Sigma Phi Eta Sigma