dahl

Lawrence F. Dahl

Email address: dahl@chem.wisc.edu

Room Number: 
8121
Telephone Number: 
608-263-2209
Group Affiliation: 
Dahl Group
Education: 

Professor Emeritus, Born 1929        
B.S. 1951, University of Louisville                 
PhD. 1956, Iowa State University

dahl's picture

Research Description

Research in the Dahl group focuses 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.

Awards and Honors

F. Albert Cotton Award in Synthetic Inorganic Chemistry 2010
Amoco Distinguished Lecturer, Indiana University 1996
Honorary Doctorate Degree, University of Louisville 1991
Recipient of Walter Hielber (70th Birthday Retirement) Lecturership, Technischen Universitate M"nchen, 1965
Appointed Kentucky Colonel by Governor of Kentucky 1982

Selected Publications

Campana CF, Guzei IA, Mednikov EG, Dahl LF. Sixty-Year Saga (1952-2013) of the Solid-State Structure of Triiron Dodecacarbonyl. Journal of Cluster Science. 2014;25:205-224.
Tan YZ, Jin S, Hamers RJ, Tainter CJ, Ni Y, Shi L, et al.. Influence of Hole-Sequestering Ligands on the Photostability of CdSe Quantum Dots
Hydrogen Bonding and OH-Stretch Spectroscopy in Water: Hexamer (Cage), Liquid Surface, Liquid, and Ice
How innocent is thallium(I)? Corrected formulations of Tl2Pd14
. Journal of Physical Chemistry C. 2013;117:313-320.
Tainter CJ, Ni Y, Shi L, Skinner JL, Mednikov EG, Dahl LF, et al.. Hydrogen Bonding and OH-Stretch Spectroscopy in Water: Hexamer (Cage), Liquid Surface, Liquid, and Ice
How innocent is thallium(I)? Corrected formulations of Tl2Pd14(CO)(9)(PMe3)(11) PF6 (2) and TlPd9(CO)(9)(PPh3)(6) PF6 clusters previously reported a
. Journal of Physical Chemistry Letters. 2013;4:12-17.
Mednikov EG, Dahl LF, Peterson AC, Russell JD, Bailey DJ, Westphall MS, et al.. How innocent is thallium(I)? Corrected formulations of Tl2Pd14(CO)(9)(PMe3)(11) PF6 (2) and TlPd9(CO)(9)(PPh3)(6) PF6 clusters previously reported as corresponding Au2Pd14 and AuPd9 clusters
Parallel Reaction Monitoring for High Resolution and High Ma
. Chemical Communications. 2013;49:1085-1087.
Mednikov EG, Dahl LF. Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo-D-2d Distorted Face-Capped Pd-14 Cubic Kernel: ((14)-M)Pd-22(CO)(20)(PEt3)(8) (+) (M=Au, Ag). Angewandte Chemie-International Edition. 2013;52:7813-7817.