Timothy R. Cook
Education and Training:
B.A., Boston University, Boston, MA (2005)
Ph.D., Massachusetts Institute of Technology, Cambridge, MA (2010)
Postdoctoral Researcher, University of Utah, Salt Lake City, UT (2010-2012)
Research Assistant Professor, University of Utah, Salt Lake City, UT (2012-2014)
Molecular self-assembly with an emphasis on coordination chemistry
Supramolecular inorganic chemistry
Catalysis focused on energy-relevant transformations
Photochemistry and spectroscopy
Coordination-driven self-assembly is a synthetic methodology capable of delivering diverse, tunable architectures, yet is currently underdeveloped as a tool to address the chemistry of energy conversion. In particular, the ability to independently design molecular subunits with specific properties which can combine into multifunctional scaffolds provides a method to generate functionally complex yet synthetically facile materials. The Cook Group exploits coordination-driven self-assembly to explore energy-relevant materials with modular photo-, redox- and catalytically active building blocks that can rapidly incorporate new molecular discoveries relevant to energy harvesting, storage, and use.
Our research program is rooted in fundamental structural, photophysical and electrochemical characterization techniques applied towards discrete supramolecular coordination complexes (SCCs) formed using the principles of molecular self-assembly and coordination chemistry. Primary thrusts include:
(1) Light Harvesting Metallacycles and Cages via Self-Assembly
The efficient capture of solar energy requires materials that strongly absorb across the visible spectrum so as to effectively match the solar flux. Chemical approaches to new light harvesting materials often rely on the organization of molecular units, inspired by nature’s photosystems. The precedent for strongly absorbing metal and organic-based molecules motivates our design of discrete supramolecular coordination complexes containing complementary chromophores.
(2) Redox-Active SCCs for Redox Flow Devices
Redox flow batteries (RFBs) break the paradigm of traditional battery designs by separating the charge carriers from the core of the device. The electrolyte chemistries of current RFBs center on small molecules and/or simple ions, which exacerbate electrolyte mixing and decomposition and offer limited tunability. We explore the synthesis and characterization of multinuclear redox-active species in the context of RFB charge carriers to interface with energy capture schemes, thereby developing a rich electrochemistry of inorganic supramolecular complexes.
(3) Coordination-Driven Self-Assembly of Cofacial Catalysts
The activation of energy-relevant small molecules is difficult owing to the multi-electron multi-proton nature of this chemistry. Polynuclear designs distribute redox and coordination demands across multiple sites which can act in concert to effect key catalytic steps. The formation of cofacial catalysts can be greatly simplified through the use of coordination-driven self-assembly, wherein two catalytic species can be tethered via distal coordination to pillar building blocks. Since the bridging pillar and catalyst platforms are independently synthesized, the size, shape, flexibility, and chemical properties of resultant cofacial complexes can be readily optimized by orthogonal adjustments, which will not significantly affect self-assembly.
Selected Recent Publications:
- Oldacre, A. N.; Friedman, A. E.; Cook, T. R.*, A Self-Assembled Cofacial Cobalt Porphyrin Prism for Oxygen Reduction Catalysis. J. Am. Chem. Soc. 2017, 139, 1424. http://dx.doi.org/10.1021/jacs.6b12404
- Kosswattaarachchi, A. M.; Friedman, A. E.; Cook, T. R.*, Characterization of a BODIPY Dye as an Active Species for Redox Flow Batteries. ChemSusChem 2016, 9, 3317. http://dx.doi.org/10.1002/cssc.201601104
- Powers, D. C.; Hwang, S. J.; Anderson, B. L.; Yang, H.; Zheng, S.-L.; Chen, Y.-S.; Cook, T. R.; Gabbaï, F. P.; Nocera, D. G., Stereoelectronic Effects in Cl2 Elimination from Binuclear Pt(III) Complexes. Inorg. Chem. 2016, 55, 11815. http://dx.doi.org/10.1021/acs.inorgchem.6b01887
- Zhang, Y.; Cox, J. M.; Friedman, A. E.; Benedict, J. B.; Cook, T. R.*, Phosphorescent Organoplatinum(II) D2A2 Metallacycles: Synthesis, Self-assembly, and Photophysical Properties. J. Coord. Chem. 2016, 69, 1914. http://dx.doi.org/10.1080/00958972.2016.1177824
- Zhou, Y.; Wang, D. P.; Zhang, Y. M.; Chitgupi, U.; Geng, J. M.; Wang, Y. H.; Zhang, Y. Z.; Cook, T. R.; Xia, J.; Lovell, J. F., A Phosphorus Phthalocyanine Formulation with Intense Absorbance at 1000 nm for Deep Optical Imaging. Theranostics 2016, 6, 688. http://dx.doi.org/10.7150/thno.14555
- Cook, T. R.*; Stang, P. J., Recent Developments in the Preparation and Chemistry of Metallacycles and Metallacages via Coordination. Chem. Rev. 2015, 115, 7001. http://dx.doi.org/10.1021/cr5005666
- Yan, X.; Cook, T. R.; Wang, P.; Huang, F.; Stang, P. J., Highly Emissive Platinum(II) Metallacages. Nat. Chem. 2015, 7, 342. http://dx.doi.org/10.1038/nchem.2201
- Cook, T. R.*; Zheng, Y.-R.; Stang, P. J., Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials. Chem. Rev. 2013, 113, 734. http://dx.doi.org/10.1021/cr3002824
- Cook, T. R.*; Vajpayee, V.; Lee, M. H.; Stang, P. J.; Chi, K.-W., Biomedical and Biochemical Applications of Self-Assembled Metallacycles and Metallacages. Acc. Chem. Res. 2013, 46, 2464. http://dx.doi.org/10.1021/ar400010v
- Cook, T. R.; McCarthy, B. D.; Lutterman, D. A.; Nocera, D. G., Halogen Oxidation and Halogen Photoelimination Chemistry of a Platinum–Rhodium Heterobimetallic Core. Inorg. Chem. 2012, 51, 5152. http://dx.doi.org/10.1021/ic300004x