Jeffrey K. Nagle
Professor of Chemistry
| Spring 2007 |
|
Phone Title Department 2nd Title 2nd Department Work Location | (207) 725-3167 Professor CHEMISTRY Chair CHEMISTRY 254 Cleaveland Hall jnagle@bowdoin.edu |
Education:
Ph. D. 1979 University of North Carolina at Chapel Hill
A. B. 1975 Earlham College, Richmond, Indiana
Research Interests
Our work is centered on the photochemistry and photophysics of luminescent platinum group molecules. Much of this effort is devoted to understanding excited state electron, energy, and atom transfer reactions, as well as exciplex (excited state complex) and excimer (excited state dimer) formation. Excited state reactions play a key role in molecular-based solar energy conversion schemes, including photosynthesis. We use optical (absorption, emission, and excitation) spectroscopies, pulsed-laser excited state lifetime measurements, and cyclic voltammetry methods to evaluate potential photocatalysts in such schemes and to test modern theories of electron transfer.
An outgrowth of this work focuses on the effect of light absorption on relativistically influenced metal-metal bond formation. Einstein's theory of special relativity governs the behavior of particles that move at speeds approaching that of light. The electrons in platinum and related atoms provide examples of such particles, and as a consequence molecules containing these atoms experience substantial relativistic effects on their interactions with light and other atoms.
An example of the type of compound we work with is provided by the molecular ion Pt2(P2O4H2)44-. This fascinating species absorbs light in the visible region of the spectrum, resulting in an intense green luminescence in water or solids. It also takes part in a rich array of photochemical reactions, including interactions with DNA, and exhibits an enhanced tendency to bond to other heavy metal atoms such as silver, gold, and thallium. Such bonding interactions result in the formation of luminescent metal-metal bonded exciplexes (excited state complexes), an area of research which my students and I have pioneered over the past several years at Bowdoin.
Publications (*indicates undergraduate coauthor)
40. Bickelhaupt F. M.; Nagle, J. K.; *Klemm, W. L. “The Role of s-p Orbital Mixing in the Bonding and Properties of Second-Period Diatomic Molecules”, J. Phys. Chem. A, 2008, 112, 2437-2446.
39. Maliarik, M.; Nagle, J. K.; Ilyukhin, A.; Murashova, E.; Mink, J.; Skripkin, M.; Glaser, J.; Kovacs, M.; Horváth “Metal-Metal Bonding in Tetracyanometallates (M = PtII, PdII, NiII) of Monovalent Thallium. Crystallographic and Spectroscopic Characterization of the New Compounds Tl2Ni(CN)4 and Tl2Pd(CN)4”, Inorg. Chem., 2007, 46, 4642-4653.
38. Yersin, H.; Donges, D.; Nagle, J. K.; Sitters, R.; Glasbeek, M. "Site-Selective Emission, Excitation, and Optically Detected Magnetic Resonance of the Pd(II) Oxinate Complex Pd(qol)2", Inorg. Chem., 2000, 39, 770-777.
Abstract
37. Nagle, J. K. "Luminescent Exciplexes and Excimers Resulting From Metal-Metal Bond Formation", Spectrum, 1999, 12 (3), 15-19.
PDF (3.1MB)
36. *Pettijohn, C. N.; *Jochnowitz, Evan B.; *Chuong, B.; Nagle, J. K.; Vogler, A. "Luminescent Excimers and Exciplexes of PtII Compounds", Coordination. Chemistry Reviews, 1998, 171, 85-92.
Abstract | PDF (357 K)
35. Donges, D.; Nagle, J. K.; Yersin, H. "Intraligand Charge Transfer in Pt(qol)2. Characterization of Electronic States by High-Resolution Shpol'skii Spectroscopy", Inorg. Chem. 1997, 36, 3040-3048.
Abstract
34. Donges, D.; Nagle, J. K.; Yersin, H. "Characterization of Intraligand Charge Transfer Transitions in Pd(qol)2, Pt(qol)2, and Pt(qtl)2 Investigated by Shpol'skii Spectroscopy", J. Luminescence 1997, 72-74, 658-659.
Bibliographic Page | Article Full Text PDF (147 KB)
33. Kratochwil, N. A.; Bednarski, P. J.; Mrozek, H.; Vogler, A.; Nagle, J. K. "Photolysis of an Iodoplatinum(IV) Diamine Complex to Cytotoxic Species by Visible Light", Anti-Cancer Drug Design 1996, 11, 155-171.
32. Kunkely, H.; Vogler, A.; Nagle, J. K. "Thermochromic Properties of Diphenyldiselenide in Solution", Inorganic Chemistry 1995, 34, 4511-4512.
First Page | Full: PDF
31. *Coldfelter, S. A.; *Doede, T. M.; *Brennan, B. A.; Nagle, J. K.; *Bender, D. P.; *Turner, W. A.; *LaPunzina, P. M. "Luminescent Metal-Metal-Bonded Exciplexes Involving Tetrakis(µ-diphosphito)diplatinate(II) and Thallium(I)", Journal of the American Chemical Society 1994, 116, 11379-11386.
First Page | Full: PDF (1019k)
30. *Bender, D. P.; Nagle, J. K. "Metal-Metal Interactions of Aqueous Lead(II) and Tin(II) Ions with the Ground and Excited States of Tetrakis(µ diphosphito)diplatinate(II)", Inorg. Chim. Acta 1994, 225, 201-205.
29. Balch, A. L.; Fung, E. Y.; Nagle, J. K.; Olmstead, M. M.; Rowley, S. P. "Lead(II)/Platinum(II) Complexes With and Without Pb-Pt Interactions", Inorg. Chem. 1993, 32, 3295-3299.
28. Nagle, J. K.; Roundhill, D. M. "Excited State Properties and Photoinduced Catalytic Reactions of Ru(bpy)32+ and Pt2(pop)44-: Outer-Sphere vs. Inner-Sphere Photochemistry", Chemtracts-Inorg. Chem. 1992, 4, 141-155.
27. Balch, A. L.; Catalano, V. J.; Chatfield, M. A.; Nagle, J. K.; Olmstead, M. M.; Reedy, P. E., Jr. "Binding of Lead(II), Antimony(III), and Other Isoelectronic Main-Group Ions to Iridium in the Metallomacrocycle Ir2(CO)2Cl2{µ-(Ph2PCH2)2AsPh}2", J. Am. Chem. Soc.1991, 113, 1252-1258.
First Page | Full: PDF (852k)
26. Assefa, Z.; DeStefano, F.; *Garepapaghi, M. A.; *LaCasce, J. H., Jr.; *Ouellete, S.; Corson, M. R.; Nagle, J. K.; Patterson, H. H. "Photoluminescence and Electronic Structure of Tl[Au(CN)2]: Evidence for Direct Thallium-Gold Interactions", Inorg. Chem. 1991, 30, 2868-2876.
25. Nagle, J. K. "Atomic Polarizability and Electronegativity", J. Am. Chem. Soc. 1990, 112, 4741-4747.
First Page | Full: PDF (872k)
24. Nagle, J. K.; *LaCasce, J. H., Jr.; Dolan, P. J., Jr.; Corson, M. R.; Assefa, Z.; Patterson, H. H. "Photoluminescence and Electronic Structures of Tl2Pt(CN)4 and Tl[Au(CN)2]: Evidence for Direct Thallium-Gold Interactions", Mol. Cryst. Liq. Cryst. 1990, 181, 359-366.
23. Ziegler, T.; Nagle, J. K.; Snijders, J. G.; Baerends, E. J.; Ravenek, W. "A Theoretical Study on the Electronic Structures and Absorption Spectra of Pt(CN)42- and Tl2Pt(CN)4 Based on Density Functional Theory Including Relativistic Effects", J. Am. Chem. Soc.1989, 111, 5631-5635.
First Page | Full: PDF (633k)
22. Balch, A. L.; Fossett, L. A.; Nagle, J. K.; Olmstead, M. M. "Nearly Linear Rh(I) Aggregates. Chemical and Spectroscopic Behavior of [Rh3(CNCH3)6{µ-(Ph2PCH2)2PPh}2]3+ and Its Oxidation Products", J. Am. Chem. Soc. 1988, 110, 6732-6738.
21. Nagle, J. K.; *Brennan, B. A. "Luminescent Exciplex Formation Involving Tetrakis(µ-diphosphito)diplatinate(II) and Thallium(I) In Aqueous Solution", J. Am. Chem. Soc. 1988, 110, 5931-5932.
First Page | Full: PDF (867k)
20. Balch, A. L.; Nagle, J. K.; Oram, D. E.; Reedy, P. E., Jr. "Oxidative Additions and Luminescence Involving Ir-Au-Ir Chains Formed by Binding of Gold(I) to the Metallomacroycle Ir2(CO)2Cl2{µ-Ph2PCH2)2AsPh}2", J. Am. Chem. Soc. 1988, 110, 454-462.
First Page | Full: PDF (1097k)
19. Nagle, J. K.; Balch, A. L.; Olmstead, M. M. "Tl2Pt(CN)4: A Noncolumnar, Luminescent Form of Pt(CN)42- Containing Pt-Tl Bonds", J. Am. Chem. Soc. 1988, 110, 319-321.
First Page | Full: PDF (378k)
18. *LaCasce, J. H., Jr.; *Turner, W. A.; Corson, M. R.; Dolan, P. J., Jr.; Nagle, J. K. "Magnetic Field Effects on the Luminescence of Cs[Au(CN)2] at Low Temperatures", Chem. Phys. 1987, 118, 289-294.
17. Balch, A. L.; Nagle, J. K.; Olmstead, M. M.; Reedy, P. E., Jr. "Formation of Luminescent, Bent Ir-Tl-Ir and Ir-Pb-Ir Chains through the Binding of Thallium(I) and Lead(II) to the Iridium Metallomacroycle Ir2(CO)2Cl2{µ-(Ph2PCH2)2AsPh}2", J. Am. Chem. Soc. 1987, 109, 4123-4124.
First Page | Full: PDF (273k)
16. *Rodman, G. S.; Nagle, J. K. "The Synthesis, Isolation, and Characterization of Tris(8-quinolinolato-N1,O8)ruthenium(III)", Inorg. Chim. Acta 1985, 105, 205-208.
15. Markert, J. T.; Blom, N.; Roper, G.; *Perregaux, A. D.; Nagasundaram, N.; Corson, M. R.; Ludi, A.; Nagle, J. K.; Patterson, H. H. "Luminescence of Cesium Dicyanoaurate(I). Evidence for Extended Au(I)-Au(I) Interactions in Two Dimensions", Chem. Phys. Lett. 1985, 118, 258-262.
14. *Reisch, G. A.; *Turner, W. A.; Corson, M. R.; Nagle, J. K. "Magnetic Field Effects on the Lifetime and Luminescence Spectrum of Tetrakis(µ-diphosphito)diplatinate(II)", Chem. Phys. Lett. 1985, 117, 561-565.
13. Nagle, J. K.; Meyer, T. J. "Flash Photolysis of a Photoactive Ruthenium Complex Mixture", Inorg. Chem. 1984, 23, 3663-3665.
12. *Heuer, W. B.; *Totten, M. D.; *Rodman, G. S.; *Hebert, E. J.; *Tracy, H. J.; Nagle, J. K. "Electron-Transfer Reactions and Luminescent Quantum Yield of the Triplet Excited State of Tetrakis[µ-diphosphito(2-)-P,P']diplatinate(II)", J. Am. Chem. Soc. 1984, 106, 1163-1164.
First Page | Full: PDF (296k)
11. Markert, J. T.; *Clements, D. P.; Corson, M. R.; Nagle, J. K. "Phosphorescent Lifetime and Quantum Yield Measurements of K4Pt2(H2P2O5)4 from 1.6 K to 300 K", Chem. Phys. Lett. 1983, 97, 175-179.
10. Durham, B.; Caspar, J. V.; Nagle, J. K.; Meyer, T. J. "Photochemistry of Ru(bpy)32+", J. Am. Chem. Soc. 1982, 104, 4803-4810.
9. Nagle, J. K.; Bernstein, J. S.; Young, R. C.; Meyer, T. J. "Charge Transfer Excited States as Molecular Photodiodes", Inorg. Chem. 1981, 20, 1760-1764.
8. Rillema, D. P.; Nagle, J. K.; *Barringer, L. F., Jr.; Meyer, T. J. "Redox Properties of Metalloporphyrin Excited States, Lifetimes, and Related Properties of a Series of para-Substituted Tetraphenylporphyrin Carbonyl Complexes of Ruthenium(II)", J. Am. Chem. Soc. 1981, 103, 56-62.
First Page | Full: PDF (940k)
7. Nagle, J. K. "Light-Induced Electron Transfer Reactions of N-Heterocyclic Ruthenium(II) Complexes", Ph. D. Thesis, University of North Carolina at Chapel Hill, Aug. 1979, 258 pp.; Avail. Univ. Microfilms Int., Order No. 8013977; Diss. Abstr. Int. B 1980, 41, 190.
6. Nagle, J. K.; Dressick, W. J.; Meyer, T. J. "Electron Transfer Reactions in the 'Abnormal' Free-Energy Region", J. Am. Chem. Soc. 1979, 101, 3993-3995.
First Page | Full: PDF (380k)
5. Bock, C. R.; Connor, J. A.; Gutierrez, A. R.; Meyer, T. J.; Whitten, D. G.; Sullivan, B. P.; Nagle, J. K. "Estimation of Excited State Redox Potentials by Electron-Transfer Quenching. Application of Electron-Transfer Theory to Excited-State Redox Processes", J. Am. Chem. Soc. 1979, 101, 4815-4824.
First Page | Full: PDF (1250k)
4. Bock, C. R.; Connor, J. A.; Gutierrez, A. R.; Meyer, T. J.; Whitten, D. G.; Sullivan, B. P.; Nagle, J. K. "Application of Electron Transfer Theory to Excited State Redox Processes", Chem. Phys. Lett. 1978, 61, 522-525.
3. Sullivan, B. P.; Abruna, H., Finklea, H. O.; Salmon, D. J.; Nagle, J. K.; Meyer, T. J.; Sprintschnik, H. "Multiple Emissions from Charge Transfer Excited States of Ruthenium(II)-Polypyridine Complexes", Chem. Phys. Lett. 1978, 58, 389-393.
2. Young, R. C.; Nagle, J. K.; Meyer, T. J.; Whitten, D. G. "Electron Transfer Quenching of Nonemitting Excited States of Ru(TPP)(py)2 and Ru(trpy)22+", J. Am. Chem. Soc. 1978, 100, 4773-4778.
First Page | Full: PDF (796k)
1. Nagle, J. K.; Young, R. C.; Meyer, T. J. "Chemically Catalyzed Disproportionation of Ru(bpy)32+*", Inorg. Chem. 1977, 16, 3366-3369.
Academic Positions and Honors
1993-present Professor, Bowdoin College
2007-2008 Visiting Research Scientist, Department of Chemistry, University of British Columbia
2003-2007 Chair, Department of Chemistry, Bowdoin College
2000-2001 Visiting Research Scientist, University of Amsterdam and Free University of Amsterdam (Porter Fellow)
1995-1998 Chair, Department of Chemistry, Bowdoin College
1993-1994 Visiting Research Scientist, University of Regensburg, Germany (Fulbright Senior Scholar)
1986-1993 Associate Professor, Bowdoin College
1986-1987 Visiting Research Scientist, Department of Chemistry, University of California at Davis
1980-1986 Assistant Professor, Bowdoin College
1979-1980 Visiting Assistant Professor of Chemistry, Bucknell University, Lewisburg, Pennsylvania
Professional Memberships
American Chemical Society (1975-present)
European Photochemistry Association (1993-present)