 Professor, Born 1929
B.S. 1951, University of Louisville
PhD. 1956, Iowa State University
Room: 6375a
Phone: 608-262-5859
Email: dahl@chem.wisc.edu
Position: Emeritus Professor
Mednikov, E.G.; Tran, N.T.; Aschbrenner, N.L.; Dahl, L.F. "Nanosized Au4Pd28(CO)22(PMe3)16 Containing 32-Atom Au4Pd28 Core-Geometry with Nearly Regular Encapsulated Au4 Tetrahedron: Proposed Multitwinned-Composite Growth-Pattern Involving Four Interpenetrating Au-Centered Cuboctahedral-Based Three-Layer (Pd3)A(AuPd6)B(Au3)C Polyhedra", J. Cluster Sci., 2007, 18, 253-269. (Special issue - dedicated to G"nter Schmid). Mednikov, E.G.; Jewell, M.C.; Dahl, L.F. "Nanosized (_12-Pt)Pd164-xPtx(CO)72(PPh3)20 (x ~ 7) Containing Pt-Centered Four-Shell 165-Atom Pd-Pt Core with Unprecedented Intershell Bridging Carbonyl Ligands: Comparative Analysis of Icosahedral Shell-Growth Patterns with Geometrically Related Pd145(CO)x(PEt3)30 (x~60) Containing Capped Three-Shell Pd145 Core", J. Am. Chem. Soc. 2007, 129, in press. deSilva, N; Laufenberg, J.W.; Dahl, L.F. "Sturctural/Bonding insights from New Geometrical Varieities of Two Pt-Au Carbonyl/Phoshine Clusters, [Pt3(AuPPh3)5(U2-CO)2L3]+ (L3=(CO)2PPh3) and [u6-Au{Pt3(u2-CO)3L4}2]+ (L=PMe3), Chem Commun., 2006, 4437-4439. de Silva, N; Fry, C.G.; Dahl, L.F. "Phosphine-Ligated Induced Formation of Thallium(I) "Full" Pt3TIPt3 Sandwich versus "Open-Face" TIPt3 Sandwich with Triangular Pt3(m2-CO)3(PR3)3 Units: Synthesis and Structural/Spectroscopic Analysis of Triphenylphosphine [(m3-TI)Pt3(m2-CO)3(PPh3)3]+ and its (m3-AuPPh3) Analogue", Dalton Trans. 2006, 1051-1059. de Silva, N.; Nichiporuk, R.V.; Dahl, L.F. "Syntheses and Structural Analyses of Variable-Stoichiometric Au-Pt-Ni Carbonyl/Phosphine Clusters, Pt3(Pt1-xNix)(AuPPh3)2(m2-CO)4(CO)(PPh3)3 and Pt2(Pt2-yNiy)(AuPPh3)2(m2-CO)4(CO)2(PPh3)2, with Ligation-Induced Site-Specific Pt/Ni Substitutional Disorder within Butterfly-Based Pt3(Pt1-xNix)Au2 and Pt2(Pt2-yNiy)Au2 Core-Geometries", Dalton Trans. 2006, 2291-2300. de Silva, N.; Dahl, L.F. " Aprotic Synthesis and Structural Determination of Nanosized Nonprotonated n3-Octahedral [Pt6Ni38(CO)48]6- Hexaanion Stablized as Cubic Solvated [NMe4]+ Salt", Inorg. Chem., 2006, 45, 8814-8816. Mednikov E.G.; Dahl, L.F. "Nanosized Au4Pd32(CO)28(PMe3)14 Containing a Highly Distorted Encapsulated Au4 Tetrahedron: Proposed Multi-Twinned Growth-Pattern from Two Deformed Au-Centered Double Icosahedral-Based Fragments," J. Cluster Sci., 2005, 16, 287-302. (Special issue-dedicated to F. A. Cotton) Mednikov E.G.; Dahl, L.F. "First High-Nuclearity Palladium Halide/Carbonyl/Phosphine Cluster, [Pd12(m3-I)2(m4-I)3(m2-CO)6(PEt3)6]+ Monocation Containing an Octacapped Octahedral Pd6(m3-Pd6(m3-I)2 Fragment: Structure-to-Synthesis Generation from Different Synthetic Routes", Inorg. Chim. Acta, 2005, 358, 1557-1570. (Special issue-dedicated to Gordon Stone). Mednikov E.G.; Fry, C.G.; Dahl, L.F. "The First Trimetallic Pd/Tl/Co Carbonyl Cluster, Trigonal [Pd9{m3-TlCo(CO)3L}(m2-CO)6(m3-CO)3L6]: Ligand-Stabilization of the Trigonal-Bipyramidal [TlCo(CO)3L] Entity", Angew. Chem. Int. Ed 2005, 44, 786-790. Mednikov E.G.; Wittayakun, J.; Dahl, L. F. "Synthesis and Stereochemical/Electrochemical Analyses of Cuboctahedral-Based Pd23(CO)x(PR3)10 Clusters (x=20 with R3=Bun3, Me2Ph; x=20, 21, 22 with R3=Et3): Geometrically Analogous Pd23(PEt3)10 Fragments with Variable Carbonyl Ligations and Resulting Implications", J. Cluster Sci., 2005, 16, 429-454. (Special issue-dedicated to Ilia I. Moiseev). de Silva, N.; Dahl, L.F. "Synthesis and Structural Analysis of First Nanosized Pt-Au Carbonyl/Phosphine Cluster, Pt13[Au2(PPh3)2]2(CO)10(PPh3)4 Containing Pt-Centered [Ph3PAu-AuPPh3]-Capped Icosahedral Pt12 Cage", Inorg. Chem. 2005, 44, 9604-9606 Mednikov, E.G.; Ivanov, S.A.; Slovokhotova, I.V.; Dahl L.F. "Formation of Two Nanosized Pd52 and Pd66 clusters, Pd52(CO)36L14 and Pd66(CO)45L16 (L=PEt3), from Hypothetical Pd38 Vertex-Truncated n3- Octahedron. "Highlighted Communication with colored Figure 1 on Internal Communication Cover" Angew. Chem. Int. Ed. 2005, 44, 6848-6854. Ivanov, S. A.; de Silva, N.; Kozee, M.A.; Nichiporuk, R.V.; Dahl, L.F. "Synthesis and Structural/Theoretical (DFT) Analysis of the Geometrically Unprecedented Au-Pt cluster, Pt7(m2-CO)8(PPh3)4(m4-AuPPh3)2: Structure-to-Synthesis Appraisal concerning its Formation", J. Cluster Sci., 2004, 15, 233-262. (Special issue-related to the Inorganic Symposium entitled, "Organometallic and Coordination Clusters and Polymers: Systems and Applications", held at London, Ontario at the 87th Canadian National Chemistry Conference, May-June, 2004). Tran, N.T.; Powell, D.R.; Dahl, L.F. "Nanosized Au2Pd41(CO)27(PEt3)15 Containing a Central Trigonal D3h Au2Pd29 Fragment Composed of Two Geometrically Unprecedented 13-Coordinated Au-Centered (m 13-Au)Pd13 Polyhedra Connected by Triangular Face-Sharing and Three Interpenetrating 12-Coordinated Pd-Centered (m12-Pd)Au2Pd10 Icosahedra: Geometrical Change in Centered Polyhedra Induced by Au/Pd Electronegativity-Mismatch", J. Chem. Soc. Dalton Trans., 2004, 209-216 Tran, N.T.; Powell, D.R.; Dahl, L.F. "Generation of AuPd22/Au2Pd21 Analogues of the High-Nuclearity Pd23(CO)20(PEt3)10 Cluster Containing 19-Atom Centered Hexacapped-Cuboctahedral (n2-octahedral) Metal Fragment: Structural-to-Synthesis Approach Concerning Formation of Au2Pd21(CO)20(PEt3)10", Dalton Trans., 2004, 217-223. (Colored Figure on Cover Page). Tran, N.T.; Dahl, L.F. "Nanosized Pd69(CO)36(PEt)18: Metal-Core Geometry Containing a Linear Assembly of Three Face-Sharing Centered Pd33 Icosahedra Inside of a Hexagonal-Shaped Pd30 Tube", Angew. Chem. Int. Ed., 2003, 42, 3533-3537. Mednikov, E.G.; Dahl, L.F. "Formation of Thallium(I) Sandwich M3TlM3 Clusters, [(m6-Tl)M6(m2-CO)6]+ (M=Pd, Pt), with Two Unconnected Triangular M3(m2-CO)3(PEt3)3 Units: Implications of Comparative Analysis of Isostructural 5d106s2 Tl(I)-(M3)2 Sandwiches (M=Pt, Pd) with known 5d10 Au(I)-(Pt3)2 Sandwich", J. Chem. Soc., Dalton Trans.,2003, 3117-3125. Mednikov, E.G.; Ivanov, S.A.; Wittayakun, J.; Dahl, L.F. "Metal-Ligated Induced Structural Interconversion between Pd23(CO)20(PEt3)10 and Pd23(CO)20(PEt3)8 Possessing Highly Dissimilar Pd23 Core-Geometries", J. Chem. Soc., Dalton Trans., 2003, 1686-1692. Mednikov, E.G.; Ivanov, S.A.; Dahl, L.F. "Pd30(CO)26(PEt3)10 and Pd54(CO)40(PEt3)14: Generation of Nanosized Pd30 and Pd54 Core-Geometries Containing Interpenetrating Cuboctahedral-Based Metal Polyhedra", Angew. Chem., Int. Ed., 2003, 42, 323-327. Ivanov, S.A.; Nichiporuk, R.V.; Mednikov, E.G.; Dahl, L.F. "First High-Nuclearity Thallium"Palladium Carbonyl Phosphine Cluster, [Tl2Pd12(CO)9(PEt3)9]2+, and Its Initial Mistaken Identity as the Unknown Au2Pd12 Analogue: Structure-to-Synthesis Approach Concerning Its Formation", J. Chem. Soc., Dalton Trans., 2002 , 4116-4127. Zhang, J.; Dahl, L. F., "First-Known High-Nuclearity Silver-Nickel Carbonyl Cluster: Nanosized [Ag16Ni24(CO)40]4- Possessing a New 40-Atom Cubic Td Closed-Packed Metal-Core Geometry", J. Chem. Soc., Dalton Trans., 2002, 1269-1274. Tran, N. T.; Kawano, M., Dahl, L.F. "High-Nuclearity Palladium Carbonyl Trimethylphospine Clusters Containing Unprecedented Face-Condensed Icosahedral-Based Transition-Metal Core-Geometries", J. Chem. Soc., Dalton Trans. 2001, 2731-2748. Kawano, M.; Bacon, J.W.; Campana, C.F.; Winger, B.E.; Dudeck, J.D.; Sirchio, S.A.; Scruggs, S.L.; Geiser, U.; Dahl, L.F., "High-Nuclearity Close-Packed Palladium-Nickel Carbonyl Phosphine Clusters: Heteropalladium [Pd16Ni4(CO)22(PPh3)4]2- and [Pd33Ni9(CO)41(PPh3)6]4- Containing Pseudo-Td ccp Pd16Ni4 and Pseudo-D3h hcp Pd33Ni9 Cores", Inorg. Chem., 2001, 40, 2554-2569. Mlynek, P.D.; Kawano, M.; Kozee, M.A.; Dahl, L.F., "First-Known High-Nuclearity Copper-Nickel Carbonyl Cluster: [CuxNi35-x(CO)40]5- (with x=3 or 5) Containing an Unprecedented 35-Atom Three-Layer hcp Triangular Stacking Metal-Core Geometry", J. Cluster Science 2001, 12, 321-346. (Special Issue dedicated to the late Dr. S. Martinengo.) Tran, N.T.; Powell, D.R.; Dahl, L.F., "Nanosized Pd145(CO)x(PET3)30 Containing a Capped Three-Shell 145-Atom Metal-Core Geometry of Pseudo Icosahedral Symmetry" Angew. Chem., Int. Ed., 2000, 39, 4121-4125. Chin G., "Pd145 Reveals Its Secrets" (Editors" Choice of the Chemistry Highlight of Recent Literature) Science, 2000, 290, 1261). Tran, N.T.; Kawano, M.; Powell, D.R.; Dahl, L.F., "High-Nuclearity [Pd13Ni13(CO)34]4- Containing a 26-atom Pd13Ni13 Core With an Unprecedented Five-Layer Close-Packed Triangular Stacking Geometry: Possible Substitutional Pd/Ni Crystal-Disorder at Specific Intralayer Nickel Sites", J. Chem. Soc., Dalton Trans., 2000, 4138"4144.
| Research Description
Research in our group continues to focus mainly on high-nuclearity homometallic and heterometallic carbonyl clusters: namely, those with at least 10 metal-core atoms containing primarily Group 10 (Ni, Pd, Pt) and Group 11 (Cu, Ag, Au) metals that form direct metal-metal bonds. It combines the art of synthesis (involving Schlenkware, preparative vac-line, and drybox techniques) with structural/bonding analyses and physical/chemical charaterization studies. Modern physical methods utilized include CCD X-ray diffraction, spectroscopic (IR, UV-Vis near IR, multinuclear NMR, ESR), mass spectrometric, magnetic susceptibility, and electrochemical measurements.
Because most of these giant-sized metal clusters possess well-defined stoichiometries and precise geometries, detailed investigations of their physical behaviors should produce insight into the onset of metallic-like character with increasing metal-core size (especially for clusters with interior atoms within their metal cores). It will be important to correlate their physical properties (e.g., variable-temperature magnetic moments and specific heats) with those of naked and ligand-stabilized nanoparticles with non-uniform size distributions. These clusters are possible precursors of new materials with useful catalytic, electronic, magnetic, optical and/or photochemical/electrochemical properties.
Recent work has given rise to a considerable number of remarkable new nanosized clusters such as: 1) three isostructural 38-atom trimetallic Au-M-Ni(M=Pd, Pt) and bimetallic Au-Ni carbonyl clusters of pseudo-D3d symmetry with substitutional Pd/Ni crystal-disorder occurring at only six equivalent metal sties (coloring problem), 2) two crystallographically superimposed Au-Ni carbonyl clusters of pseudo-D4d symmetry containing the same 26-atom gold cage (with either one or two interior Au prisoners) surrounded by 40 Ni atoms that are ligated by 56 COs, and 3) a three-shell palladium carbonyl phosphine cluster of pseudo-icosahedral symmetry containing 55 interior Pd atoms in the first two shells encapsulated by a 60-vertex 3rd shell polyhedron ( a geometrical metalloisomer of C60 buckyball) with 30 additional capping Pd atoms.
The diversity of research, in which coworkers are encouraged to develop and broaden their own research projects and to carry out 'operational tests' of their hypotheses in the laboratory, generates a highly stimulating environment with extensive cross-fertilization of ideas and much give-and-take interaction occurring between group members. The following publications illustrate some of our research.
Last Updated: September 17, 2003
F. Albert Cotton Award in Synthetic Inorganic Chemistry, 2010 Recipient of the Pioneer Award of the American Institute of Chemists, 2000 Recipient of the Willard Gibbs Medal, Chicago ACS Section, 1999 Recipient of the Hans B. Jonassen Lectureship, Tulane University, 1998 Recipient of the Gordon Stone Lectureship, Bristol University, 1997 Amoco Distinguished Lecturer, Indiana University, 1996 Recipient of Frontiers in Chemistry Lectureship, Texas A & M University (3 lectures), 1996 Recipient of the 5th Fred Basolo Lectureship and Medal, Northwestern University, 1995 Major Lecturer at Robert A. Welch Foundation Conference on Nanochemistry, 1995 Recipient of the Hilldale Award in the Physical Sciences at the University of Wisconsin-Madison, 1994 Elected Fellow of American Academy of Arts and Sciences, 1992 Appointed Hilldale Chair Professor by the University of Wisconsin System Board of Regents, 1991 Recipient of Honorary Doctorate Degree, University of Louisville, 1991 Recipient of the First Alumnus Award from the College of Arts and Sciences, University of Louisville, 1990 Recipient of the 1990 J. C. Bailar, Jr. Lectureship and Medal, University of Illinois-Urbana Champaign 1990 Recipient of the Paolo Chini Lectureship endowed by the Italian Society of Chemistry, Fall 1989 Recipient of the H. Willard Davis Lectureship, University of S. Carolina, 1989 Elected to the National Academy of Sciences, 1988 Recipient of the P. C. Reilly Lectureship, University of Notre Dame, 1987 Recipient of a Senior U.S. Scientist Humboldt Award by the Alexander von-Humboldt-Stiftung, 1985 Recipient of the Sir Ronald Nyholm Lectureship and Medal, Royal Society of Chemistry, 1985-86 Named Distinguished Alumnus of the College of Letters and Science, University of Louisville, 1983 Recipient of the Brotherton Research Professorship, University of Leeds, 1983 Appointed "Kentucky Colonel" by Governor of Kentucky, 1982 Elected Fellow of the AAAS, 1980 UW-Chair Professorship, July 1978 (Named after the late Robert E. Rundle, in recognition of former thesis advisor at Iowa State University) Elected Fellow of the New York Academy of Sciences, 1975 American Chemical Society Award in Inorganic Chemistry, 1974 Edgar Fahs Smith Memorial Lecturer, University of Pennsylvania, 1971 First H.L. Ritter Memorial Lecurer, Miami University (Ohio), 1971 First Distinguished Alumni Lecturer in Chemistry, University of Louisville, 1969 Guggenheim Fellow, 1969-1970 Recipient of Walter Hielber (70th Birthday Retirement) Lecturership, Technischen Universitate M"nchen, 1965 Alfred P. Sloan Foundation Fellow, 1963-65 Recipient of Kazuo Nakamoto Distinguished Lectureship, Marquette University, 1944
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