Machan Research Group

Inorganic chemistry focused on catalysis related to energy, electrochemistry, spectroelectrochemistry, and materials chemistry



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Research @ UVA

30. Inverse Potential Scaling in Co-Electrocatalytic Activity for CO2 Reduction Through Redox Mediator Tuning and Catalyst Design

Reid, A.G.; Moreno, J.J.; Hooe, S.L.; Baugh, K.R.; Thomas, I.H.; Dickie, D.A.; Machan, C.W.* Chem. Sci. 2022 DOI: 10.1039/D2SC03258A

29. Homogeneous Catalytic Reduction of O2 to H2O by a Terpyridine-Based FeN3O Complex

Cook, E.N.; Hooe, S.L.; Dickie, D.A.; Machan, C.W.* Inorg. Chem. 2022 DOI: 10.1021/acs.inorgchem.2c00524
**Featured Article

28. Bioinspired Mononuclear Mn Complexes for O2 Activation and Biologically Relevant Reactions

Cook, E.N.; Machan, C.W.* Dalton Trans. 2021 DOI: 10.1039/D1DT03178C

**HOT Article

27. Mediated Inner-Sphere Electron Transfer Induces Homogeneous Reduction of CO2 via Through-Space Electronic Conjugation

Hooe, S.L.; Moreno, J. J.; Reid, A.G.; Cook, E.N.; Machan, C.W.* Angew. Chemie, Int. Ed. 2022 DOI: 10.1002/anie.202109645

Corrigendum 61: e202205139

**VIP Designation

26. Catalytic Reduction of Dioxygen to Water by a Bioinspired Non-Heme Iron Complex via a 2+2 Mechanism

Cook, E.N.; Dickie, D.A.; Machan, C.W.* J. Am. Chem. Soc. 2021 DOI: 10.1021/jacs.1c04572

25. Pendent Relay Enhances H2O2 Selectivity during Dioxygen Reduction Mediated by Bipyridine-Based Co–N2O2 Complexes

Nichols, A.W.; Cook, E.N.; Gan, Y.J.; Miedaner, P.R.; Dressel, J.M.; Dickie, D.A.; Shafaat, H.S.; Machan, C.W.* J. Am. Chem. Soc. 2021 DOI: 10.1021/jacs.1c03381

24. Non-covalent Assembly of Proton Donors and p-benzoquinone Anions for Co-electrocatalytic Reduction of Dioxygen

Hooe, S.L.; Cook, E.N.; Reid, A.G.; Machan, C.W.* Chem. Sci. 2021 DOI: 10.10139/D1SC01271A

23. Electrocatalytic Water Oxidation by a Trinuclear Copper(II) Complex

Geer, A. M.; Musgrave III, C.; Webber, C.; Nielsen, R. J.; McKeown, B. A.; Liu, C.; Schleker, P. P. M.; Jakes, P.; Jia, X.; Dickie, D. A.; Granwehr, J.; Zhang, S.; Machan, C. W.*; Goddard, W. A.*; Gunnoe, T. B.*, ACS Catal. 2021 DOI: 10.1021/acscatal.1c01395.

22. DFT Study on the Electrocatalytic Reduction of CO2 to CO by a Molecular Chromium Complex

Moreno, J.J; Hooe, S.H.; Machan, C.W.* Inorg. Chem. 2021 DOI: 10.1021/acs.inorgchem.0c03136

21. Soluble, Crystalline, and Thermally Stable Alkali CO2 and Carbonite (CO22–) Clusters Supported by Cyclic(Alkyl)(Amino) Carbenes

Freeman, L.A.; Obi, A.D.; Machost, H.R.; Molino, A.; Nichols, A.W.; Dickie, D.A.; Wilson, D.J.D.*; Machan, C.W.*; Gilliard Jr., R.J.* Chem. Sci. 2021 DOI: 10.1039/D0SC06851A

20. Reduction of dioxygen to water by a Co(N2O2) complex with a 2,2′-bipyridine backbone​

Nichols, A.W.; Kuehner, J.S.; Huffman, B.L.; Miedaner, P.R.; Dickie, D.A.; Machan, C.W.* Chem. Commun. 2021 DOI: 10.1039/D0CC06763F

19. Controlling Polymorphism and Orientation of NU-901/NU-1000 Metal–Organic Framework Thin Films

Verma, P.K.; Huelsenbeck, L.; Nichols, A.W.; Islamoglu, T.; Heinrich, H.; Machan, C.W.; Giri, G.* Chem. Mater. 2020 DOI: 10.1021/acs.chemmater.0c03539

18. Mechanistic Insight into Initiation and Regioselectivity in the Copolymerization of epoxides and anhydrides by Al Complexes

Popowski, Y.; Moreno, J.J.; Nichols, A.W.; Hooe, S.L.; Bouchey, C.J.; Rath, N.P.; Machan, C.W.*; Tolman, W.B.* Chem. Commun. 2020 DOI: 10/10339/D0CC05652A

17. Electrocatalytic CO2 Reduction to Formate with Molecular Fe(III) Complexes Containing Pendent Proton Relays

Nichols, A.W.; Hooe, S.L.; Kuehner, J.S.; Dickie, D.A.; Machan, C.W.* Inorg. Chem. 2020 DOI:

16. Advances in the Molecular Catalysis of Dioxygen Reduction

Machan, C.W.* ACS Catal. 2020 DOI: 10.1021/acscatal.9b04477 

15. Electrochemical CO2 Reduction in a Continuous Non-Aqueous Flow Configuration with [Ni(cyclam)]2+ Catalyst​

Jiang, C.; Nichols, A.W.; Walzer, J.F.; Machan, C.W.* Inorg. Chem. 2020 DOI: 10.1021/acs.inorgchem.9b03171

14. Highly Efficient Electrocatalytic Reduction of CO2 to CO by a Molecular Chromium Complex​

Hooe, S.L.; Dressel, J.M.; Dickie, D.A.; Machan, C.W.* ACS Catal. 2020 DOI: 10.1021/acscatal.9b04687

13. Catalytic Reduction of O2 to H2O2 via a Mn Complex

Hooe, S.L.; Machan, C.W.* Trends in Chemistry - Mechanism of the Month 2019 DOI:

12. Secondary-Sphere Effects in Molecular Electrocatalytic CO2 Reduction

Nichols, A.W.; Machan, C.W.* Front. Chemi. - Inorg. Chem. 2019 DOI: 10.3389/fchem.2019.00397

11. Electrocatalytic Reduction of Dioxygen by Mn(III) meso-Tetra(N-methylpyridinium-4-yl)porphyrin in Universal Buffer

Lieske, L.E.; Hooe, S.L.; Nichols, A.W.; Machan, C.W.* Dalton Trans. 2019 DOI: 10.1039/C9DT01436E

**HOT Article

10. Metal-Organic Frameworks as Porous Templates for Enhanced Cobalt Oxide Electrocatalyst Performance 

Huelsenbeck, L.; Hooe, S.L.; Ghorbanpour, A.; Conley, A.M.; Heinrich, H.; Machan, C.W.*; Giri, G.* ACS Appl. Energy Mat. 2019 DOI: 10.1021/acsaem.9b00127

9. A Look at Periodic Trends in d-Block Molecular Electrocatalysts for CO2 Reduction

Jiang, C.; Nichols, A.W.; Machan, C.W.* Dalton Trans. 2019 DOI: 10.1039/C9DT00491B

8. Recent Advances in Spectroelectrochemistry Related to Molecular Catalytic Processes

Machan, C.W.* Curr. Opin. Electrochem. 2019 DOI: 10.10.1016/j.coelec.2019.03.010

7. Metal-Free Electrochemical Reduction of Carbon Dioxide Mediated by Cyclic(Alkyl)(Amino) Carbenes

Lieske, L.E.†; Freeman, L.A.†; Wang, G.; Dickie, D.A.; Gilliard Jr., R.J.*; Machan, C.W. * Chem. – Eur. J. 2019 DOI: 10.1002/chem.201900316

6. Dioxygen Reduction to Hydrogen Peroxide by a Molecular Mn Complex: Mechanistic Divergence Between Homogeneous and Heterogeneous Reductants

Hooe, S.L. and Machan, C.W. J. Am. Chem. Soc. 2019 DOI: 10.1021/jacs.8b13373

5. Nitric oxide activation facilitated by cooperative multimetallic electron transfer within an iron-functionalized polyoxovanadate–alkoxide cluster​

Li, F.; Meyer, R.L.; Carpenter, S.H.; VanGelder, L.E.; Nichols, A.W.; Machan, C.W.; Neidig, M.L.; Matson, E.M.* Chem. Sci. 2018 DOI: 10.1039/C8SC00987B 

4. Electrochemical Reduction of Carbon Dioxide with a Molecular Polypyridyl Nickel Complex

Lieske, L.E.; Rheingold, A.L.; Machan, C.W.* Sust. Energy Fuels 2018 DOI: 10.1039/C8SE00027A

3. Reversible Modulation of the Redox Characteristics of Acid-Sensitive Molybdenum and Tungsten Scorpionate Complexes

Heyer, A.J.; Shivokevich, P.J.; Hooe, S.L.; Welch, K.D.; Harman, W.D.; Machan, C.W. Dalton Trans. 2018 DOI:10.1039/C8DT00598B

2. Electrocatalytic Reduction of CO2 to Formate by an Iron Schiff Base Complex

Nichols, A.W.; Chatterjee, S.; Sabat, M.; Machan, C.W. Inorg. Chem. 2018, DOI: 10.1021/acs.inorgchem.7b02955

1. Electrocatalytic Reduction of Dioxygen to Hydrogen Peroxide by a Molecular Manganese Complex with a Bipyridine-Containing Schiff Base Ligand

Hooe, S.L.; Rheingold, A.L.; Machan, C.W. J. Am. Chem. Soc. 2018, DOI: 10.1021/jacs.7b09027


Postdoctoral Research

17. Charged Macromolecular Rhenium Bipyridine Catalysts with Tunable CO2 Reduction Potentials
Sahu, S.; Cheung, P.L.; Machan, C.W.; Chabolla, S.A.; Kubiak, C.P.; Gianneschi, N.C. Chem. – Eur. J. 2017, DOI: 10.1002/chem.201701901

16. Concerted One-Electron Two-Proton Transfer Processes in Models Inspired by the Tyr-His Couple of Photosystem II
Huynh, M.R.; Mora, S.J.; Villalba, M.; Tejeda-Ferrari, M.E.; Liddell, P.A; Cherry, B.R.; Teillout, A.-L.; Machan, C.W.; Kubiak, C.P.; Gust, D.; Moore, T.A.; Hammes-Schiffer, S.; Moore, A.L. ACS Cent. Sci. 2017, DOI: 10.1021/acscentsci.7b00125

15. Bio-inspired CO2 reduction by a rhenium tricarbonyl bipyridine-based catalyst appended to amino acids and peptidic platforms: incorporating proton relays and hydrogen-bonding functional groups
Chabolla, S.A.; Machan, C.W.; Yin, J.; Dellamary, E.A.; Sahu, S.; Gianneschi, N.C.; Gilson, M.K.; Tezcan, F.A.; Kubiak, C.P. Faraday Discuss. 2017, DOI: 10.1039/c7fd00003k

14. Electrocatalytic Reduction of Carbon Dioxide with Mn(terpyridine) Carbonyl Complexes
Machan, C.W.; Kubiak, C.P. Dalton Trans. 201645, 17179

13. Interrogating Heterobimetallic Co-Catalytic Responses for the Electrocatalytic Reduction of CO2 Using Supramolecular Assembly
Machan, C.W.; Kubiak, C.P. Dalton Trans. Special Issue on 'Reactions Facilitated by Ligand Design' 2016, 45, 15942

12. Improving the Efficiency and Activity of Electrocatalysts for the Reduction of CO2 Through Supramolecular Assembly with Amino Acid-Modified Ligands
Machan, C.W.; Yin, J.; Chabolla, S.A.; Gilson, M.K.; Kubiak, C.P. J. Am. Chem. Soc. 2016, 138, 8184

11. Re(I) NHC Complexes for Electrocatalytic Conversion of CO2
Stanton III, C.J.; Machan, C.W.; Vandezande, J.E.; Jin, T.; Majetich, G.; Schaefer III, H.F.; Kubiak, C.P.; Li, G.; Agarwal, J. Inorg. Chem. 2016, 55, 3136

10. Photocatalytic Reduction of Carbon Dioxide to CO and HCO2H Using fac-Mn(CN)(bpy)(CO)3
Cheung, P.L.; Machan, C.W.; Malkhasian, Y.S.; Agarwal, J.; Kubiak, C.P. Inorg. Chem. 2016, 55, 3192

9. Rapid synthesis of redox-active dodecaborane B12(OR)12 clusters under ambient conditions
Wixtrom, A.I.; Shao, Y.; Jung, D.; Machan, C.W.; Kevork, S.N.; Qian, E.A.; Axtell, J.C.; Khan, S.I.; Kubiak, C.P.; Spokoyny, A.M. Inorg. Chem. Front. (Emerging Investigator Issue) 2016, 3, 711

8. Orientation of Immobilized Cyano-Substituted Bipyridine Re(I) fac-Tricarbonyl Electrocatalysts on Au Surfaces
Clark, M.L.; Rudshteyn, B.; Ge, A.; Chabolla, S.A.; Machan, C.W.; Psciuk, B.T.; Song, J.; Canzi, G.; Lian, T.; Batista, V.S.; Kubiak, C.P. J. Phys. Chem. C 2016, 120, 1657

7. Electrocatalytic Reduction of Carbon Dioxide by Mn(CN)(2,2ʹ-bipyridine(CO)3: CN Coordination Alters Mechanism
Machan, C.W.; Stanton III, C.J.; Vandezande, J.E.; Majetich, G.F.; Schaefer III, H.F; Kubiak, C.P.; Agarwal, J. Inorg. Chem. 2015, 54, 8849

6. Reductive Disproportionation of Carbon Dioxide by an Alkyl-Functionalized Pyridine Monoimine Re(I) fac-tricarbonyl Electrocatalyst
Machan, C.W.; Chabolla, S.A.; Kubiak, C.P. Organometallics 2015, 34, 4678

5. A Molecular Ruthenium Electrocatalyst for the Reduction of Carbon Dioxide to CO and Formate
Machan, C.W.; Sampson, M.D.; Kubiak, C.P. J. Am. Chem. Soc. 2015, 137, 8564

4. Synthesis, Spectroscopy, and Electrochemistry of (α-diimine)M(CO)3Br, M = Mn, Re, Complexes: Ligands Isoelectronic to Bipyridyl Show Differences in CO2 Reduction
Vollmer, M.; Machan, C.W.; Clark, M.L.; Antholine, W.; Agarwal, J.; Schaefer, H.F.; Kubiak, C.P; Walensky, J. Organometallics 2015, 34, 3

3. Supramolecular Assembly Promotes the Electrocatalytic Reduction of Carbon Dioxide by Re(I) Bipyridine Catalysts at a Lower Overpotential
Machan, C.W.; Chabolla, S.A.; Yin, J.; Gilson, M.K.; Tezcan, F.A.; Kubiak, C.P. J. Am. Chem. Soc. 2014, 136, 14598

2. Combined Steric and Electronic Effects of Positional Substitution on Dimethyl-Bipyridine Rhenium(I) Tricarbonyl Electrocatalysts for the Reduction of CO2
Chabolla, S.A.; Dellamary, E.A.; Machan, C.W.; Tezcan, F.A.; Kubiak, C.P. Inorg. Chim. Acta 2014, 422, 109

1. Developing a Mechanistic Understanding of Molecular Electrocatalysts for CO2 Reduction Using Infrared Spectroelectrochemistry
Machan, C.W.; Sampson, M.D.; Chabolla, S.A.; Dang, T.; Kubiak, C.P. Organometallics 2014, 33, 4550

Graduate Research

7. General Strategy for the Synthesis of Rigid Higher-Order Platinum(II) Complexes via the Weak-Link Approach: Tweezers, Triple-Layers and Macrocycles
Kennedy, R.D.; Machan, C.W.; McGuirk, C.M.; Rosen, M.S.; Stern, C.L.; Mirkin, C.A. Inorg. Chem. 2013, 52, 5876

6. One-Pot Synthesis of an Fe(II) Bisterpyridine Complex with Allosterically Regulated Electronic Properties
Machan, C.W.; Adelhardt, M.; Sarjeant, A.A.; Stern, C.L.; Sutter, J.; Meyer, K.; Mirkin, C. A. J. Am. Chem. Soc. 2012, 134, 16921

5. Crystallographic Snapshots of the Bond-Breaking Isomerization Reactions of Ni(II) Complexes with Hemilabile Ligands
Machan, C.W.; Lifschitz, A.M.; Sarjeant, A.A.; Stern, C.L.; Mirkin, C.A.; Angew. Chem., Int. Ed. 2012, 51, 1469

4. A Coordination Chemistry Dichotomy for Icosahedral Carborane-Based Ligands
Spokoyny, A.M.; Machan, C.W.; Clingerman, D.J.; Rosen, M.S.; Wiester, M.J.; Kennedy, R.D.; Sarjeant, A.A.; Stern, C.L.; Mirkin, C.A.; Nat. Chem. 2011, 3, 590 Highlight by A. Weller, ibid.

3. Plasticity of the Nickel (II) Coordination Environment in Complexes with Hemilabile Phosphino Thioether Ligands
Machan, C.W.; Spokoyny, A.M.; Jones, M.R.; Sarjeant, A.A.; Stern, C.L.; Mirkin, C.A. J. Am. Chem. Soc. 2011, 33, 3023

2. Chelating Effect as a Driving Force for the Selective Formation of Heteroligated Pt(II) Complexes with Bidentate Phosphino-Chalcoether Ligands
Rosen, M.S.; Spokoyny, A.M.; Machan, C.W.; Stern, C.; Sarjeant, A.A.; Mirkin, C.A.; Inorg. Chem. 2011, 50, 1411

1. Electronic Tuning of Nickel-Based Bis(dicarbollide) Redox Shutles in Dye-Sensitized Solar Cells
Spokoyny, A.M.; Li, T.C.; Farha, O.K.; Machan, C.W.; She, C.; Marks, T.J.; Hupp, J.T.; Mirkin, C.A.; Angew. Chem., Int. Ed. 2010, 49, 5339