Location: Bowdoin / Jeffrey K. Nagle

Chemistry

Jeffrey K. Nagle

Charles Weston Pickard Professor of Chemistry

Contact Information

jnagle@bowdoin.edu
207-725-3167
Chemistry
254 Cleaveland Hall


Fall 2013

  • Introductory Chemistry I (CHEM 101B)


Jeffrey K. Nagle: Bowdoin: Chemistry

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 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, an area of research that my students and I have pioneered over the past several years at Bowdoin.



42.  Roberts, M. N.; Carling, C.-J.; Nagle, J. K.; Branda, N. R.; Wolf, M. O. "Successful Bifunctional Photoswitching and Electronic Communication of Two Platinum(II) Acetylide Bridged Dithienylethenes", J. Am. Chem. Soc. 2009, 131, 16644-16645.

41. Roberts, M.N.; Nagle, J.K.; Finden, J.G.; Branda, N.R.; Wolf, M.O. "Linker-Dependent Metal-Sensitized Photoswitching of Dithienylethenes", Inorg. Chem., 2009, 48, 19-21.

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 = Pt(II), Pd(II), Ni(II) 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", Coord. Chem. Rev., 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", Inorg. Chem. 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)", J. Am. Chem. Soc. 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.

*indicates undergaduate co-author

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)

Jason Iskarpatyoti* '09
Computational and Experimental Studies of Tris-(3,3'-bis(5,6-dimethyl-1,2,4-Triazine))ruthenium(II)  and Related Compounds

Jonathan Freedman '08
Theoretical and Experimental Investigation of the Photodecompostion of Water by Tl(III) and Hg(II) with at Platinum(II) Dimer

Robert Adam Kinney* '05
Photocatalytic Decomposition of Methanol by Thallium(III) and Mercury(II) with a Platinum(II) Dimer

Andrew C. Berical* '05
Photocatalytic Oxidation of Water by Mercury(II) and Thallium(III) with a Platinum (II) Dimer

Brian Grandjean* '04
Lanthanoid(III) Ion Interactions with a Photoluminescent Platinum(II) Dimer

Jocelyn Foulke '05
Effects of Group 3 and 4 d-Block Metal Ions on the Luminescence of a Platinum Dimer in Aqueous Solution (Fall 2002)

Colin Heinle* '03
Luminescent Exciplex Formation Between Al3+, Ga3+, and In3+ Ions and a Platinum Dimer in Aqueous Solution

Brian Grandjean '04
Lanthanoid(III) Ion Interactions with a Photoluminescent Platinum(II) Dimer (summer 2002, Spring 2003)

William Klemm '04
Computational Studies of a Platinum(II) Dimer and Related Species with the Amsterdam Density Functional (ADF) Program (summer 2002)

Lauren Webb* '00
Luminescent Exciplex Formation Between a Platinum(II) Dimer and Compounds of Ag(I) and Au(I)

Evan Jochnowitz* '99
Luminescent Exciplex Formation Between a Platinum(II) Dimer and Compounds of Ag(I) and Au(I)

Colin Segovis '99
Luminescent Exciplex Formation Between a Platinum(II) Dimer and Ag(I)

Tanya Freedman '99
A Photoluminescent Iridium Analog of Tetrakis[µ-diphosphito(2-)-P,P']diplatinate(II)

Christine Jefferis* '98
Luminescent Exciplex Formation Between a Platinum(II) Dimer and Aqueous Silver(I) Ions

Bao Chuong* '97
Excimer Formation of Dicyano(4,7-diphenyl- 1,10-phenanthroline)platinum(II) and Exciplex Formation Involving Tetrakis(µ-diphosphito)diplatinate(II) and Dicyanoaurate(I)

Bradford J. Pistorio* '97
Photochemical Reactions of Pt2(pop)44- in Methanol and Aqueous Solutions of Mercury(II)

Russell A. Grubbs '96
Photo-assisted Solvent Decomposition and Reduction of Hg(II) by Pt2(P2O5H2)44-: Evidence for the Formation of Common Intermediates Generated in Water and Methanol

Cheryl N. Pettijohn* '96 Eximer vs. Exciplex Formation with Thallium(I) and a Platinum(II) Dimer

Jodie K. Chin* '93 Spectroscopic Studies of Dialkyldithiocarbamates of Thallium(I), Lead(II), and Bismuth(III)

Christopher J. Ziegler* '92
Catalytic Oxidation of Water and Methanol by   Mercury(II) with a Platinum(II) Dimer

Sarah A. Clodfelter* '91
Luminescent Exciplex Formation Between Thallium(I), Silver(I), and a Platinum(II) Dimer

David P. Bender '91
Excited State Interactions of a Platinum(II) Dimer with Several p-Block Metal Ions

Tina M. Doede* '90
Luminescent Exciplex Formation Between Thallium(I), Silver(I), and a Platinum(II) Dimer

Paul M. LaPunzina* '88
A Study of the Interactions Between Tetrakis- (µ-diphosphito)diplatinate(II) in Concentrated Thallium(I) Solution

‡Mohammad A. Garepapaghi* '87
Studies of Photoluminescence and Magneto- Photoluminescence Properties of Thallium   Dicyanoaurate at Low Temperatures

‡Jonathan T. Fanburg* '87 Studies of Photoluminescence and Magneto-photoluminescence Properties of Uranyl Nitrate Dihydrate at 4.2, 77, and 300 K

Nancy S. Demcak* '86 Excited State Electron Transfer Reactions of Pt2(P2O5H2)44- with Aromatic Amines in Solution

Robert J. Hinkle* '86
Photochemical Redox Reactions Involving Mercuric Ion and Tetrakis[µ-diphosphito]diplatinate(II)

Jennifer W. Izard* '86
Lanthanide Quenching of Tetrakis[µ-diphosphito(2-)-P,P']diplatinate(II)

Bridget A. Brennan* '86
Exciplex Formation Between the Excited State of a Platinum(II) Dimer and Thallium(I)

†Joseph H. LaCasce, Jr. '86
Comparisons Between the Low-Temperature Photoluminescence of Cs[Au(CN)2] and TlAu(CN)2

Marion A. Ryder* '85
The Application of Group Theory to Chemistry

Elizabeth H. Johnson* '85
Excited State Quenching of Tetrakis[ µ-diphosphito(2-)-P,P']diplatinate(II) by Aromatic Amines

Daniel S. Pratt* '85
Extended Metal-Metal Interactions Between Tetrakis[µ-diphosphito(2-)-P,P']diplatinate(II)   and Mercury(II)

Andrew L. Meyer* '85
Computer-Controlled Potentiometric Titration

†Michael W. Kopp* '85
Magnetic Field Effects on the Photoluminescent Liifetime and Spectrum of Cs[Au(CN)2] at Low Temperature

Mark D. Totten* '84
Excited State Electron Transfer Reactions of Tetrakis[µ-diphosphito(2-)-P,P']diplatinate(II)

Brian J. Rowe '84
Synthesis and Analysis of Some Complexes of Platinum with Bis(2-pyridylmethyl)ketazine and 3,6-Bis(2'-pyridyl)pyridazine

Justin T. Gerstle, Jr.* '84
Cyclic Voltammetric Investigation of Ruthenium(II) Complexes with Triazine Ligands

Marcia L. Meredith* '84
History of Quantum Theory

†George A. Reisch* '84
Magnetic Field Effects on Intensity and Peak Position of K4[Pt2(P2O5H2)4] Phosphorescence Spectra

†Warren A. Turner* '84
Magnetic Field Effects on the Photoluminescent Lifetime of K4[Pt2(P2O5H2)4] at Low Temperatures

Eugene Sung, Jr.* '83
Synthesis and Characterization of Platinum and Palladium Ligand-Bridged Metal Dimers

Everett H. Billingslea '83
Experimental Studies of K2[FeO4] and Sr[FeO4]

Eric J. Hebert* '83
Determination of the Excited-State Reduction Potential of a Platinum Dimer

Harold F. Caswell* '83
Synthesis of Some Organometallic Complexes with Bis(2-pyridylmethyl)ketazine and 3,6-Bis(2'-pyridyl)pyridazine

†Adrian D. Perregaux* '83
An Investigation into the Phosphorescent Structure of the 458 nm Emitting Level of Cs[Au(CN)2]

†Kathleen A. Hartnett* '83
An Examination of the Photoluminescent Properties of Four Concentrations of Bis(8-Quinolinolato)platinum(II) in DMF Over the Temperature Range 1.7 K to 220 K

Tory S. Bagshaw '82
A Comparison of the Luminescence Properties of Th(sqol)4, Th(qol)4 and Pt(qol)-2

Adam W. Cerel '82
Spectroscopic, Cyclic Voltammetric and pH-dependent Studies of the Metalloflavin Complex cis-bis(2,2'-bipyridine)riboflavinruthenium(II) Tetrafluoroborate

Kirk D. Hutchinson '82
Preparation and Properties of New Luminescent N-Heterocyclic Complexes of Ruthenium(II)

†David P. Clements* '82
Luminescent Lifetimes of K4[Pt2(P2O5H2)4] Over the Temperature Range 1.55 K to 300 K

Henry J. Tracy* '81
The Synthesis and Characterization of Some Ligand-Bridged Metal Dimers

James L. Goss '81
The Stopped-Flow Method of Determining Rate Constants of Fast Reactions

Jozsef P. Urmos '81
Late-Pleistocene Paleotemperature Analysis Using the Sr Content of Mytilus Edulis

William B. Heuer* '81
Estimation of the Excited-State Redox Potentials for Several Platinum-Group Metal Complexes

Gary S. Rodman* '81
Synthesis and Charracterization of Some Ruthenium 8-Quinolinolato Complexes

‡Supervised by Professor Dale Syphers of the Bowdoin College Physics Department; the projects were collaborative efforts between Professor Syphers and me.

†Supervised by Professor Michael Corson of the Bowdoin College Physics Department; the projects were collaborative efforts between Professor Corson and me.