About

Professor Gregory S. Girolami received his B.S. degrees in chemistry and physics from the University of Texas at Austin and earned his Ph.D. from the University of California at Berkeley. Following his doctoral studies, he was a NATO postdoctoral fellow with Sir Geoffrey Wilkinson at Imperial College of Science and Technology before joining the faculty at the University of Illinois in 1983. His research primarily focuses on the synthesis, properties, and reactivity of new inorganic, organometallic, and solid state species. Professor Girolami's work encompasses four main areas: mechanistic studies of organometallic reactions such as the activation of alkanes, the synthesis of new molecule-based magnetic materials, chemical vapor deposition of thin films from designed molecular precursors, and the design of artificial photosynthetic centers. His research interests include the synthesis of transition metal complexes for use as catalysts, precursors for chemical vapor deposition of thin films, and building blocks for novel magnetic materials, as well as organometallic chemistry and catalysis. Throughout his career, Professor Girolami has been recognized with several honors including the Office of Naval Research Young Investigator Award, Sloan Foundation Fellowship, Dreyfus Teacher-Scholar Award, and University Scholar Award.

Research topics

• Organic chemistry
• Chemistry
• Medicinal chemistry
• Metallurgy
• Geology
• Mathematics
• Nanotechnology
• Inorganic chemistry
• Crystallography
• Geometry
• Materials science
• Chemical engineering

Selected publications

• MgH2 thin films and nanowires deposited by CVD from a magnesium diamidodiboranate precursor

  Materials Today Communications · 2026-01-01

  articleOpen access

  Magnesium hydride, MgH 2 , is deposited by chemical vapor deposition (CVD) at substrate temperatures of 140-300 °C from the newly synthesized magnesium diamidodiboranate precursor, Mg(NMe 2 BH 2 NMe 2 BH 3 ) 2 , abbreviated Mg(NBNB) 2 . The resulting films are pure, single-phase MgH 2 as evidenced by X-ray diffraction and Raman spectroscopy. Depending on the growth conditions, the morphology of the deposits can be varied from a granular film to islands to a continuous film with either protruding pillars or nanowires. The deposits are nanocrystalline and consist of pure, polycrystalline α-MgH 2 under all conditions. The formation of MgH 2 from Mg(NBNB) 2 is thought to involve a hydrogen elimination mechanism involving the BH 2 or BH 3 groups.

  PublisherDOI

• Precision nanoscience aided by multimodal observations

  MRS Bulletin · 2025-10-23

  articleOpen access

  Abstract This article discusses precision nanoscience, a new frontier in material chemistry, where multimodal observation and engineering focus on understanding the intricate details of atomic structures as they evolve, interact, and influence chemical properties and processes. These advancements are crucial for addressing societal challenges in sustainability, energy, and material synthesis while driving technological innovation. Specifically, we cover the emergence of precision nanoscience in nanocrystals, two-dimensional materials, and device integration, as well as the understanding of surfaces and interfaces of these nanoscale systems, some through the recently developed liquid phase transmission electron microscopy (LPTEM). We present a unified vision for broad access to cutting-edge materials chemistry and nanoscience research, highlight the case studies across diverse material classes utilizing or advancing LPTEM, and identify the critical issues that warrant deeper discussion. In alignment with the Centers for Chemical Innovation by the National Science Foundation, we envision the approach of a Multimodal Observatory for Single Atom Imaging of Chemistry to push for the future development of precision nanoscience. Graphical abstract

  PublisherOA PDFDOI

• Weakly Bound but Strongly Interacting: The Structures, Stabilities, and Dynamics of Osmium(II) Ethane, Propane, and Butane Complexes

  Journal of the American Chemical Society · 2025-02-25 · 5 citations

  articleSenior authorCorresponding

  Low-temperature protonation of the osmium(II) alkyl compounds (C5Me5)Os(dfmpm)R, where dfmpm = (F3C)2PCH2P(CF3)2 and R = ethyl, n-propyl, n-butyl, or i-butyl, generates σ-ethane, σ-propane, σ-n-butane, and σ-i-butane complexes. The alkane dissociation barriers are ∼13.2 kcal mol–1 or about 0.5 kcal mol–1 larger than that of the previously described methane complex [(C5Me5)Os(dfmpm)(CH4)]+. The alkane ligands bind to osmium through one methyl group, which exchanges slowly with the unbound terminal methyl group(s). Within the bound methyl group, one bridging hydrogen atom interacts directly with osmium; it exchanges rapidly with the other two methyl C–H bonds at a rate consistent with a slightly hindered C–C bond rotation. The large difference in 1JCH between the bridging (75 Hz) and terminal (142 Hz) C–H sites is consistent with the view that the 16-electron [Cp*Os(dfmpm)]+ fragment has partially abstracted a hydride group (H–) from the alkane, which confers carbocation (sp2) character to the CH2R portion of the Os–H–CH2R unit. The extent of this distortion and the overall strength of the metal-alkane interaction are correlated with the alkane C–H orbital energies in a manner consistent with covalent metal–ligand bonding. Whereas most ligands can bind to metals with little structural reorganization, an alkane must undergo a significant structural change─weakening of a C–H bond─to become a sufficiently good donor and acceptor to bind to a metal. Collectively, these results show that the binding energies of alkane ligands are small not because the constituent metal–ligand interactions are weak but rather because the reorganization energy needed to form them is large.

  PublisherDOI

• Synthesis, characterization, and thermal properties of volatile 1,4-dialkyl-5-silatetrazolines: nitrogen-rich silicon heterocycles as possible CVD precursors for silicon nitride

  Dalton Transactions · 2025-01-01

  articleOpen accessSenior authorCorresponding

  The synthesis and properties of three 1,4-dialkyl-5-silatetrazoline compounds ( t BuNCHCHN t Bu)Si(N 4 R 2 ) are described, where R = Et, i Pr, or t Bu. These compounds may be useful as low temperature CVD precursors for silicon nitride thin films.

  PublisherOA PDFDOI

• Top-down reorganization of self-assembled monolayers on Au(111)

  Nanotechnology · 2025-08-28

  articleOpen access

  Bottom-up synthesis of graphene nanoribbons (GNRs) from aryl halide precursors is often performed thermally or in-solution, without detailing the local molecular assembly or the precursor's response to electromechanics perturbation. This synthetic approach forms nanoribbons with well-defined widths and atomically precise edges, which are necessary for ensuring bandgap uniformity. However, neither on-surface nor solution-based GNR synthesis techniques adequately address the problem of positional control, which is crucial to the fabrication of GNR transistors. To better understand this issue, we investigate the on-surface ordering of 10, 10'-dibromo-9, 9'-bianthracene (DBBA), the 7A-GNR monomer precursor. Scanning tunneling microscopy imaging shows that DBBA molecules spontaneously assemble on Au(111) into non-covalent two-dimensional islands. By varying sample temperature during and after deposition, we observe three different adsorbate arrangements. These two-dimensional packing structures demonstrate differing responses to localized excitations. The difference in packing structures and their respective responses to electro-mechanical perturbations can give us insight into how to best optimize conditions for locally controlled and large-scale thermal GNR polymer growth.

  PublisherDOI

• Synthesis, Characterization, and Thermolysis Studies of Binary Malondialdehydate Complexes of Copper(II) and Palladium(II)

  Chemistry of Materials · 2025-05-23

  articleSenior authorCorresponding

  An improved preparation of the malondialdehydate (mda) salt Na(mda)(H2O) is reported; also described are preparations of copper(II) and palladium(II) complexes of mda and its 2-phenylmalondialdehydate (2-Ph-mda) analog. Crystal structures of Na(mda)(H2O), Cu(mda)2, Cu(2-Ph-mda)2, Pd(mda)2, and Pd(2-Ph-mda)2 are described, along with nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) data. Cu(mda)2 and Pd(mda)2 deposit metallic thin films at 130 °C under chemical vapor deposition (CVD) conditions. Mechanistic studies show that Cu(mda)2 transforms to copper metal by means of a ligand fragmentation pathway that involves carbon–carbon bond scission reactions.

  PublisherDOI

• MgH2 Thin Films and Nanowires Deposited by CVD from a Magnesium Diamidodiboranate Precursor

  SSRN Electronic Journal · 2025-01-01

  preprintOpen access
  PublisherDOI

• MgH2 Thin Films and Nanowires Deposited by CVD from a Magnesium Diamidodiboranate Precursor

  SSRN Electronic Journal · 2025-01-01

  preprintOpen access
  PublisherDOI

• Response to the rebuttal of the article <i>Pathological crystal structures</i>

  Acta Crystallographica Section C Structural Chemistry · 2024-06-13 · 1 citations

  articleOpen accessSenior author

  We stand fully behind our earlier suggestion [Raymond & Girolami (2023). Acta Cryst. C79, 445-455] that the claim by Fish and co-workers [Chen et al. (1995). J. Am. Chem. Soc. 117, 9097-9098; Smith et al. (2014). Organometallics, 33, 2389-2404] of a linear two-coordinate rhodium(I) species is incorrect, and that the putative rhodium atom is in fact silver.

  PublisherOA PDFDOI

• Measuring the Magnetic Anisotropy of Metal–Metal Multiple Bonds: The Importance of Correcting for Ligand Effects

  Inorganic Chemistry · 2024-08-14

  articleSenior authorCorresponding

  We describe the synthesis and characterization of the quadruply-bonded dimer Mo2(CH2NMe2BH3)4 in which each molybdenum(II) center is bound to two chelating boranatodimethylaminomethyl (BDAM) ligands. The BDAM anions bind to the metal at one end by a metal–carbon σ bond and at the other by a three-center M–H–B interaction. Each BDAM ligand chelates to a single Mo atom so that the metal–metal bond is unbridged; the Mo–Mo distance is 2.114(2) Å. Structural and solution NMR data, analyzed via McConnell’s equation and supported by DFT calculations, show that the magnetic anisotropies associated with highly polarizable and π-bonding ligands (such as chloride groups and aryl rings) can greatly affect the NMR chemical shifts of reporter groups, so that ignoring their contributions leads to significant overestimates of the anisotropy due just to the metal–metal bond. We propose a method to quantify and correct for the magnetic anisotropy effects arising from the ligands. Application of this method to Mo2(BDAM)4 indicates that the magnetic anisotropy of the Mo–Mo quadruple bond in this molecule is about −800 × 10–36 m3 molecule–1. Anisotropies significantly higher than this value (as sometimes reported in the prior literature) are most likely incorrect.

  PublisherDOI

Recent grants

• Exploratory Synthesis and Reactivity of Volatile Transition Metal Complexes and Use as Molecular Precursors

  NSF · $390k · 2014–2018

• Chemical Vapor Deposition of Metallic Films at Low Temperatures: Precursor Synthesis and Hydrogen-Assisted Reaction Chemistry

  NSF · $605k · 2004–2007

• Exploratory Synthesis and Reactivity of Volatile Transition Metal Complexes and Use as Molecular Precursors

  NSF · $480k · 2017–2020

• Volatile Transition Metal Compounds with New Ligand Archetypes: Exploratory Synthesis, Small Molecule Reactivity, and Use as Molecular Precursors

  NSF · $390k · 2011–2014

• Exploratory Synthesis and Reactivity of Volatile Transition Metal Complexes and Use as Molecular Precursors

  NSF · $495k · 2020–2024

Frequent coauthors

• Scott R. Daly

  University of Iowa

  92 shared

• John R. Abelson

  University of Illinois Urbana-Champaign

  87 shared

• Do Young Kim

  Chungnam National University

  45 shared

• Ralph G. Nuzzo

  45 shared

• Christopher L. Gross

  41 shared

• Sumeng Liu

  40 shared

• Andrew C. Dunbar

  University of Illinois Urbana-Champaign

  36 shared

• Brian J. Bellott

  SUNY Fredonia

  34 shared

Awards & honors

• Office of Naval Research Young Investigator Award
• Sloan Foundation Fellowship
• Dreyfus Teacher-Scholar Award
• University Scholar Award