Gregory S. Girolami

Gregory S. Girolami[1] (born October 16, 1956) is the William H. and Janet G. Lycan Professor of Chemistry at the University of Illinois Urbana-Champaign. His research focuses on the synthesis, properties, and reactivity of new inorganic, organometallic, and solid state species. Girolami has been elected a fellow of the American Association for the Advancement of Science,[2] the Royal Society of Chemistry,[3] and the American Chemical Society.[4]

Gregory Scott Girolami
Born1956 (age 66–67)
Alma materUniversity of Texas at Austin B.S.
University of California at Berkeley Ph.D. (1981)
Scientific career
FieldsChemistry
InstitutionsUniversity of Illinois at Urbana–Champaign
ThesisAlkyl and Lewis-Base Derivatives of Compounds which contain Multiple Metal-Metal Bonds (1981)
Doctoral advisorRichard A. Andersen
Other academic advisorsGeoffrey Wilkinson
Doctoral studentsCheon Jinwoo, Wenbin Lin,[5] Julia L. Brumaghim,[6] Timothy H. Warren[7]
Websitefaculty.scs.illinois.edu/girolami/

Early life and education

He was born in 1956[8] in Honolulu, Hawaii, and grew up in California, Mexico, and Missouri. He started college at the age of 16, and four years later received B.S. degrees both in chemistry and in physics from the University of Texas at Austin.[9] He obtained his Ph.D. in 1981 from the University of California, Berkeley with Prof. Richard A. Andersen. Girolami's doctoral research centered on the chemistry of quadruply-bonded dinuclear transition metal complexes.[10][11][12] Thereafter, he was a NATO postdoctoral fellow with Sir Geoffrey Wilkinson at the Imperial College of Science and Technology, and his work there focused on the synthesis and chemistry of first-row transition metal-alkyl complexes.[13][14][15]

Independent career

Girolami joined the faculty of the University of Illinois at Urbana-Champaign in 1983. He has served as Head of the Chemistry Department twice, first from 2000 until 2005 and again from 2013 to 2016.

He is the author of several textbooks, including X-ray Crystallography[9] and Synthesis and Technique in Inorganic Chemistry.[16] He was the co-editor of volume 36 of Inorganic Syntheses.[17]

Girolami is also co-founder of a university spin-off company, Tiptek LLC, which manufactures ultrasharp probe tips for use in scanning tunneling microscopy and for fault diagnosis and testing of integrated circuits. The company has patented its field-directed sputter sharpening (FDSS) technology, which was originally developed in the laboratories of Girolami and fellow UIUC Professor Joseph Lyding.[18]

Research

To date, Girolami's independent research career has encompassed five major themes: mechanistic studies of organometallic reactions such as the polymerization of alkenes and the activation of saturated alkanes, the chemical vapor deposition of thin films from designed molecular precursors, the construction and study of molecular analogs of the photosynthetic reaction center, actinide chemistry, and the synthesis of new molecule-based magnetic materials. His research approach emphasizes the synthesis of new inorganic and organometallic compounds and materials, investigations of their mechanisms of formation, and measurements and interpretations of their physical properties.

Organometallic chemistry

Girolami's early work focused on the synthesis of transition metal compounds with metal-hydrogen and metal-carbon bonds, especially those possessing unusual electronic structures. In 1989, Girolami and Morse showed that [Zr(CH
3)
6]2−
 was of trigonal prismatic molecular geometry as indicated by X-ray crystallography.[19] This rare molecular geometry was attributed to second-order Jahn-Teller distortions in this d0 metal complex. Girolami's group accurately predicted that other d0 ML6 species such as [Nb(CH
3)
6]−
, [Ta(CH
3)
6]−
, and W(CH3)6 would also prove to have trigonal prismatic geometry.[19] Girolami also discovered the first titanium alkyl/alkene complex in 1993, which models the key intermediate in Ziegler-Natta catalysis.[20] Later model studies of C-H, B-H, and Si-H activation by transition metal complexes led to his current work on approaches to the isolation of stable alkane complexes.

Chemical vapor deposition

In the mid-1980s Girolami began research on the chemical vapor deposition (CVD) of thin films, especially of phases containing transition metals. Girolami studied the chemical design of new CVD precursors. He investigated copper(I) compounds for copper CVD,[21] an approach that is now a key fabrication step for integrated circuits.[22] His mechanistic studies of CVD processes involved transition metals, and these efforts have recently resulted in the development of low-temperature CVD to achieve the deposition of conformal thin films, in work carried out in collaboration with Professor John Abelson of Illinois' Department of Materials Science and Engineering.[23] Most recently, he discovered a new class of highly volatile CVD precursors containing the aminodiboranate ligand.[24][25]

Molecular analogs of the photosynthetic reaction center

In a now-concluded project, Girolami studied the chemistry and photophysics of bis(porphyrinate) metal sandwich complexes in collaboration with Illinois Professor of Chemistry Kenneth S. Suslick. These complexes were proposed to mimic the conversion of light to chemical energy in photosynthesis. Girolami's group synthesized bis(porphyrin) complexes of thorium, uranium,[26] zirconium,[27] and hafnium, and showed that these complexes displayed photophysical properties similar to those of the “special pair”, a chlorophyll dimer present in the photosystem I reaction center.[28]

Actinide chemistry

Overlapping with Girolami's interest in bis(porphryin) complexes that mimic the photosynthetic reaction center, the Girolami group has also studied actinide chemistry.[29]

Magnetic materials

In the mid-1990s, Girolami began an investigation of the synthesis of new magnetic solids via a building block approach, publishing in Science in 1995.[30] Girolami also reported metal-substituted analogs of Prussian blue that have magnetic ordering temperatures above 100 °C.[31]

Awards

Girolami has received numerous awards for his research, including the Office of Naval Research Young Investigator Award, a Sloan Foundation Fellowship, a Dreyfus Teacher-Scholar Award, and a University Scholar Award.[32] He has been honored by UIUC with a Campus Award for Excellence in Graduate and Professional Teaching, for the introduction of a graduate class in inorganic chemistry covering group theory and electronic correlation methods.[33][34]

References
  1. "Link to Dr. Girolami's webpage at the Department of Chemistry at the University of Illinois at Urbana-Champaign".
  2. Kloeppel, James E. "Eleven professors at Illinois elected as 2007 AAAS Fellows". news.illinois.edu. Retrieved 2021-06-01.
  3. "Greetings from the Department Head | Chemistry at Illinois". chemistry.illinois.edu. Retrieved 2021-06-01.
  4. "2013 ACS Fellows". 2020-09-23. Archived from the original on 2020-09-23. Retrieved 2021-06-01.
  5. "Wenbin Lin CV (2018)" (PDF).
  6. chemistry.sites.clemson.edu https://chemistry.sites.clemson.edu/brumaghimgroup/boss.html. Retrieved 2021-05-19. {{cite web}}: Missing or empty |title= (help)
  7. "Tim Warren". The Warren Group. Retrieved 2021-05-19.
  8. "Girolami, Gregory S. 1956-".
  9. "X-Ray Crystallography, by Gregory S. Girolami, published by University Science Books". www.uscibooks.com. Retrieved 2021-05-31.
  10. Girolami, Gregory S.; Mainz, Vera V.; Andersen, Richard A. (1980-04-01). "Coordination complexes of tetrakis(trifluoroacetato)dimolybdenum. A solution proton, fluorine-19, and phosphorus-31 nuclear magnetic resonance and infrared spectroscopic study". Inorganic Chemistry. 19 (4): 805–810. doi:10.1021/ic50206a004. ISSN 0020-1669.
  11. Girolami, Gregory S.; Andersen, Richard A. (1981-07-01). "Reaction of binuclear carboxylate complexes of molybdenum, rhenium, ruthenium, and rhodium with tert-butyl isocyanide: metal-metal bond cleavage vs. bond retention". Inorganic Chemistry. 20 (7): 2040–2044. doi:10.1021/ic50221a022. ISSN 0020-1669.
  12. Girolami, Gregory S.; Mainz, Vera V.; Andersen, Richard A.; Vollmer, Sara H.; Day, Victor W. (1981-07-01). "Quadruply bonded tetramethyltetrakis(trialkylphosphine)dimolybdenum compounds: phosphine exchange kinetics, acetone formation with carbon monoxide and crystal structure of Mo2Me4(PMe3)4". Journal of the American Chemical Society. 103 (13): 3953–3955. doi:10.1021/ja00403a069. ISSN 0002-7863.
  13. Girolami, Gregory S.; Salt, Julian E.; Wilkinson, Geoffrey; Thornton-Pett, Mark; Hursthouse, Michael B. (1983-09-01). "Alkyl, hydride, and dinitrogen 1,2-bis(dimethylphosphino)ethane complexes of chromium. Crystal structures of Me2Cr(dmpe)2, CrH4(dmpe)2, and Cr(N2)2(dmpe)2". Journal of the American Chemical Society. 105 (18): 5954–5956. doi:10.1021/ja00356a060. ISSN 0002-7863.
  14. Girolami, Gregory S.; Wilkinson, Geoffrey; Thornton-Pett, Mark; Hursthouse, Michael B. (1983-10-01). "Hydrido, alkyl, and ethylene 1,2-bis(dimethylphosphino)ethane complexes of manganese and the crystal structures of MnBr2(dmpe)2, [Mn(AlH4)(dmpe)2]2 and MnMe2(dmpe)2". Journal of the American Chemical Society. 105 (22): 6752–6753. doi:10.1021/ja00360a054. ISSN 0002-7863.
  15. Girolami, Gregory S.; Wilkinson, Geoffrey; Galas, Anita M. R.; Thornton-Pett, Mark; Hursthouse, Michael B. (1985-01-01). "Synthesis and properties of the divalent 1,2-bis(dimethylphosphino)ethane (dmpe) complexes MCl2(dmpe)2 and MMe2(dmpe)2(M = Ti, V, Cr, Mn, or Fe). X-Ray crystal structures of MCl2(dmpe)2(M = Ti, V, or Cr), MnBr2(dmpe)2, TiMe1.3Cl0.7(dmpe)2, and CrMe2(dmpe)2". Journal of the Chemical Society, Dalton Transactions (7): 1339–1348. doi:10.1039/DT9850001339. ISSN 1364-5447.
  16. "Synthesis and Technique in Inorganic Chemistry, A Laboratory Manual, Gregory S. Girolami, Thomas B. Rauchfuss, Robert J. Angelici". www.uscibooks.com. Retrieved 2021-05-31.
  17. "Inorganic Syntheses, Volume 36 | Wiley". Wiley.com. Retrieved 2021-05-31.
  18. Schmucker, S. W.; Kumar, N.; Abelson, J. R.; Daly, S. R.; Girolami, G. S.; Bischof, M. R.; Jaeger, D. L.; Reidy, R. F.; Gorman, B. P.; Alexander, J.; Ballard, J. B. (2012-07-03). "Field-directed sputter sharpening for tailored probe materials and atomic-scale lithography". Nature Communications. 3 (1): 935. Bibcode:2012NatCo...3..935S. doi:10.1038/ncomms1907. ISSN 2041-1723. PMID 22760634.
  19. Morse, P. M.; Girolami, G. S. (1989). "Are d0 ML6 complexes always octahedral? The X-ray structure of trigonal-prismatic [Li(tmed)]2[ZrMe6]". J. Am. Chem. Soc. 111 (11): 4114. doi:10.1021/ja00193a061.
  20. Spencer, Michael D.; Morse, Paige M.; Wilson, Scott R.; Girolami, Gregory S. (1993-03-01). "Preparation, catalytic reactivity, and x-ray crystal structure of the first Group 4 alkyl/alkene complexes. The first structural models of the key Ziegler-Natta catalytic intermediate". Journal of the American Chemical Society. 115 (5): 2057–2059. doi:10.1021/ja00058a073. ISSN 0002-7863.
  21. Girolami, Gregory S.; Jeffries, Patrick M.; Dubois, Lawrence H. (1993). "Mechanistic studies of copper thin-film growth from CuI and CuII .beta.-diketonates". Journal of the American Chemical Society. 115 (3): 1015–1024. doi:10.1021/ja00056a028. ISSN 0002-7863.
  22. Gordon, Peter G.; Kurek, Agnieszka; Barry, Seán T. (2014-12-09). "Trends in Copper Precursor Development for CVD and ALD Applications". ECS Journal of Solid State Science and Technology. 4 (1): N3188–N3197. doi:10.1149/2.0261501jss. ISSN 2162-8769. S2CID 97668427.
  23. Abelson, John R.; Girolami, Gregory S. (2020-04-09). "New strategies for conformal, superconformal, and ultrasmooth films by low temperature chemical vapor deposition". Journal of Vacuum Science & Technology A. 38 (3): 030802. Bibcode:2020JVSTA..38c0802A. doi:10.1116/6.0000035. ISSN 0734-2101.
  24. Daly, Scott R.; Kim, Do Young; Yang, Yu; Abelson, John R.; Girolami, Gregory S. (2010-02-24). "Lanthanide N,N-Dimethylaminodiboranates: Highly Volatile Precursors for the Deposition of Lanthanide-Containing Thin Films". Journal of the American Chemical Society. 132 (7): 2106–2107. doi:10.1021/ja9098005. ISSN 0002-7863. PMID 20108908.
  25. Daly, Scott R.; Kim, Do Young; Girolami, Gregory S. (2012-07-02). "Lanthanide N,N-Dimethylaminodiboranates as a New Class of Highly Volatile Chemical Vapor Deposition Precursors". Inorganic Chemistry. 51 (13): 7050–7065. doi:10.1021/ic201852j. ISSN 0020-1669. PMID 22686567.
  26. Girolami, Gregory S.; Gorlin, Philip A.; Milam, Stanley N.; Suslick, Kenneth S.; Wilson, Scott R. (1994-06-01). "Bis(porphyrin)actinide Complexes and Their Radical Cations and Dications". Journal of Coordination Chemistry. 32 (1–3): 173–212. doi:10.1080/00958979408024247. ISSN 0095-8972.
  27. Girolami, Gregory S.; Hein, Christopher L.; Suslick, Kenneth S. (1996). "A Zirconium Bis(porphyrinate) Sandwich Complex with an Appended Quinone". Angewandte Chemie International Edition in English. 35 (11): 1223–1225. doi:10.1002/anie.199612231. ISSN 1521-3773.
  28. Girolami, Gregory S.; Gorlin, Philip A.; Suslick, Kenneth S. (1994-02-01). "Electronically asymmetric bis(porphyrin) sandwich complexes". Inorganic Chemistry. 33 (4): 626–627. doi:10.1021/ic00082a002. ISSN 0020-1669.
  29. Bilsel, Osman; Rodriguez, Juan; Milam, Stanley N.; Gorlin, Philip A.; Girolami, Gregory S.; Suslick, Kenneth S.; Holten, Dewey (1992-07-01). "Electronic states and optical properties of porphyrins in van der Waals contact: thorium(IV) sandwich complexes". Journal of the American Chemical Society. 114 (16): 6528–6538. doi:10.1021/ja00042a037. ISSN 0002-7863.
  30. Entley, William R.; Girolami, Gregory S. (1995-04-21). "High-Temperature Molecular Magnets Based on Cyanovanadate Building Blocks: Spontaneous Magnetization at 230 K". Science. 268 (5209): 397–400. Bibcode:1995Sci...268..397E. doi:10.1126/science.268.5209.397. ISSN 0036-8075. PMID 17746547. S2CID 10784183.
  31. Holmes, Stephen M.; Girolami, Gregory S. (1999-06-01). "Sol−Gel Synthesis of KVII[CrIII(CN)6]·2H2O: A Crystalline Molecule-Based Magnet with a Magnetic Ordering Temperature above 100 °C". Journal of the American Chemical Society. 121 (23): 5593–5594. doi:10.1021/ja990946c. ISSN 0002-7863.
  32. "Gregory S. Girolami | Chemistry at Illinois". chemistry.illinois.edu. Retrieved 2021-06-01.
  33. Bureau, News. "Faculty, staff and teaching assistants honored with Campus Awards for Excellence in Instruction". news.illinois.edu. Retrieved 2021-06-01. {{cite web}}: |first= has generic name (help)
  34. "Greg Girolami recognized for excellence in teaching | Chemistry at Illinois". chemistry.illinois.edu. Retrieved 2021-06-01.
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