Research Network for Metals in Medicine

 

 

Professor Robert Stranger

BSc(Hons), PhD(Tas), DipEd

Position: Professor, Chemistry

Affiliation: The Australian National University, Department of Chemistry

Postal Address:
Department of Chemistry
The Faculties
Australian National University
Canberra ACT 0200
AUSTRALIA

Phone: +61 (02) 6125 2934
Email: Rob.Stranger@anu.edu.au
Webpage: http://chemistry.anu.edu.au/staff/RS/home.html


Research Profile

The applicant’s contributions have mainly been in the field of physical inorganic chemistry and computational quantum chemistry dealing with the electronic structure, bonding and spectroscopy of transition metal complexes, particularly bimetallic systems exhibiting magnetic interactions or metal-metal bonding. Contributions include:

  • developing a theoretical model to successfully assign the extremely complex electronic spectra of the classic metal-metal bonded Mo2X93- (X = Cl, Br) dimer system, a spectroscopic problem that had existed for over 20 years.
  • developing a covalency-modified ligand-field model for predicting the electronic spectra of transition metal complexes involving strongly covalent metal-ligand bonds.
  • pioneering the use of DFT methods combined with the broken-symmetry approach, to calculate the structures and properties of a wide variety of polynuclear metal complexes.
  • showing that the broken-symmetry/DFT methodology provides a reliable and conceptually appealing framework in which to investigate metal-metal interactions ranging from weak antiferromagnetic coupling through to strong metal-metal bonding.
  • undertaking a systematic study of periodic trends in metal-metal bonding in dinuclear systems which revealed surprisingly simple but important trends and allowed quantification of the electronic factors affecting metal-metal bonding.
  • establishing the connection between high-spin/low-spin crossover and metal-metal bond formation in d4d4 and d5d5 dinuclear systems.
  • establishing the connection between the novel ferromagnetic crossed-exchange mechanism and high-spin/low-spin crossover in mixed-valence manganese and iron dinuclear complexes.
  • showing that in heteronuclear bimetallic systems, it is possible, through judicious choice of the metal ions, to tune the magnetic properties over a large range of interactions from strongly antiferromanetic through to strong ferromagnetic coupling.
  • applying broken-symmetry/DFT methods to investigate the structures and magnetic properties of polynuclear manganese complexes which model the metal sites of a number of important biological oxomanganese systems.
  • using broken-symmetry/DFT methods to study the mechanism of dioxygen elimination and cleavage in oxomanganese complexes which model the oxygen-evolving centre of Photosystem II.
  • using DFT to investigate the energetics and mechanisms of small molecule (N2, NO and CO) activation and cleavage in sterically-hindered three-coordinate transition metal complexes.


Selected Publications

  1. Butler, S.E., Smith, P.W., STRANGER, R and Grey, I.E. Halogen Ordering in Cs3Cr2Cl6Br3: a Spectroscopic Study. Inorganic Chemistry, 25, 4375-4378, 1986.
  2. Smith, P.W. and STRANGER, R. Vibrational Spectra of Salts of Type A3[Mo2X9], with X=Cl,Br,I. Australian Journal of Chemistry, 39, 1269-1280, 1986.
  3. Grey, I.E., Madsen, I.C., Butler, S.E., Smith, P.W. and STRANGER, R. Halogen Ordering in Tricesium Tribromohexachlorodichromate. Acta Crystallographica, C42, 769-771, 1986.
  4. Dubicki, L., Krausz, E.R., STRANGER, R., Smith, P.W. and Tanabe, Y. Electronic Spectrum of Cs3Mo2Cl9. Inorganic Chemistry, 26, 2247-2254, 1987.
  5. STRANGER, R., Grey, I.E., Madsen, I.C. and Smith, P.W. Structure Systematics in A3Mo2X9, X=Cl,Br,I, from Rietveld Refinement of X-ray Powder Data. Journal of Solid State Chemistry, 69, 162-170, 1987.
  6. Hitchman, M.A., Lichon, M., McDonald, R.G., Smith, P.W., STRANGER, R., Skelton, B.W. and White, A.H. Crystal and Molecular Structure of CrSO4.5H2O and Single Crystal Electronic Spectra and Bonding of CrSO4.5H2O, CuSO4.5H2O and CuSO4.5D2O. Journal of the Chemical Society, Dalton Transactions, 1817-1822, 1987.
  7. Hitchman, M.A., McDonald, R.G., Smith, P.W. and STRANGER, R. Electronic Spectrum and Metal-Ligand Bonding Parameters of the V(H2O)63+ Ion. Journal of the Chemical Society, Dalton Transactions, 1393-1395, 1988.
  8. STRANGER, R., Sirat, K., Smith, P.W., Grey, I.E. and Madsen, I.C. Structure, Vibrational and Electronic Spectra, and Bonding in Trans-Diaquabis(oxalato)Vanadate(III) Complex Salts, A[V(C2O4)2(H2O)2].xH2O, A=Cs,K,MeNH3. Journal of the Chemical Society, Dalton Transactions, 2245-2253, 1988.
  9. STRANGER, R., Smith, P.W. and Grey, I.E. Magneto-Structural Correlations and Metal-Metal Bonding in Exchange-Coupled A3Mo2X9 (X=Cl,Br,I) Complexes. Inorganic Chemistry, 28, 1271-1278, 1989.
  10. STRANGER, R. On the Assignment of Doubly-Excited Pair Transitions in the Electronic Spectrum of Cs3Mo2Cl9. Chemical Physics Letters, 157, 472-478, 1989.
  11. STRANGER, R., Moran, G., Krausz, E., Güdel, H. and Furer, N. Octahedral Monomeric Mo(III): A Magneto-optical Study of Mo3+ Doped in Cs2NaYCl6.Molecular Physics, 69, 11-31, 1990.
  12. STRANGER, R. Role of the Trigonal t2e2-nen Single-Ion Configuration in d3d3 Metal-Metal m Bonded Dimers. Inorganic Chemistry, 29, 5231-5237, 1990.
  13. McDonald, R.G., STRANGER, R. Hitchman, M.A. and Smith, P.W. Unusual Features in the Polarised Single Crystal Electronic Spectrum of (NH4)2[V(H2O)6](SO4)2: Analysis of Fano Antiresonance Structure and Bonding in the V(H2O)62+ Complex. Chemical Physics, 154, 179-192, 1991.
  14. STRANGER, R., Moran, G., Krausz, E., Dubicki, L., Güdel, H. and Furer, N. Optical Study of the Near-Infrared Emission and Absorption in the Strongly Exchange-Coupled Dimer Cs3Mo2Cl9. Inorganic Chemistry, 31, 2860-2864, 1992.
  15. Donlevy, T.M., Gahan, L.R., Hambley, T.W. and STRANGER, R. Synthesis and Spectroscopic Properties of the Encapsulated Cobalt(III) Complexes Derived from the Unsymmetrically Substituted Ligand 5-Methyl-5-(4-amino-2-azabutyl)-3,7-dithianonane-1,9-diamine (N4S2). Inorganic Chemistry, 31, 4376-4382, 1992.
  16. Grey, I.E. and STRANGER, R. Structure Determination of aTiOSO4 from Powder X-ray Diffraction Data. Journal of Solid State Chemistry, 101, 331-339, 1992.
  17. STRANGER, R., Wallis, S.C., Gahan, L.R., Kennard, C.H.L. and Byriel, K.A. A Spectroscopic and Ligand-Field Analysis of the Spin-Orbit Interaction Between the 1Eg and 3T2g States in bis(1,4,7-triazacyclononane)Ni(II). Journal of the Chemical Society, Dalton Transactions, 2971-2976, 1992.
  18. Bruce, J.I., Gahan, L.R., Hambley, T.W. and STRANGER, R. Enforced Coordination of Chromium(III) to a Thioether Donor in an Encapsulated Complex. Journal of the Chemical Society, Chemical Communications, 702-704, 1993.
  19. Donlevy, T.M., Gahan, L.R., Hambley, T.W., McMahon, K.L. and STRANGER, R. Synthesis, Spectroscopy and Structure of the Cobalt(III) Complex of the Hexadentate Ligand 5-Methyl-5-(4-amino-2-thiabutyl)-3,7-dithianonane-1,9-diamine. Australian Journal of Chemistry, 46, 1799-1809, 1993.
  20. STRANGER, R., Moran, G., Krausz, E., and Medley, G. Magneto-Optical Investigation of the Broad Spin-Allowed Bands in the Metal-Metal Bonded Complexes Mo2X93- (X=Cl,Br). Inorganic Chemistry, 32, 4555-4560, 1993.
  21. Bruce, J.I. Gahan, L.R., Hambley, T.W. and STRANGER, R. Synthesis, Structure and Spectroscopy of Encapsulated Complexes of Co(III) Derived from the Ligand 5-Methyl-5-(4-amino-2-thiabutyl)-3,7-diazanonane-1,9-diamine (N5S). Inorganic Chemistry, 32, 5997-6002, 1993.
  22. Donlevy, T.M., Gahan, L.R., Byriel, K.A., Kennard, C.H.L. and STRANGER, R. Synthesis, Structure and Spectroscopy of an Encapsulated Nickel(II) Complex of the Unsymmetrical Macrobicyclic Ligand 1-Amine-8-methyl-6,10-dithia-3,13,16,19-tetraazabicyclo[6.6.6] icosane (AMN4S2sar). Inorganic Chemistry, 32, 6023-6027, 1993.
  23. Medley, G.A. and STRANGER, R. Study of the Electronic Structure, Metal-Metal Bonding and Ground State Exchange Coupling in Face-Shared Mo2X93- (X=Cl,Br,I) Dimers Using the Broken-Symmetry Xm-CH3CO2)4(H2O)2]A2 (A=ClO4-,CF3SO3-). Inorganic Chemistry, 34, 5646-5655, 1995.
  24. STRANGER, R., Medley, G.A., McGrady, J.E., Garrett, J.M., Appleton, T.G. and Heath, G.A. Electronic Structure of [Pt2(m-O2CCH3)4(H2O)2]2+ Using the Quasi-Relativistic Xa-SW Method: Analysis of Metal-Metal Bonding, Assignment of Electronic Spectra and Comparison with Rh2(m-O2CCH3)4(H2O)2. Inorganic Chemistry, 35, 2268-2275, 1996.
  25. Lovell, T., McGrady, J.E., STRANGER, R. and Macgregor, S.A. Optimised Geometries of Bimetallic Systems using Density Functional Theory: a Comparison of the Molecular Orbital and Broken-Symmetry Approaches. Inorganic Chemistry, 35, 3079-3080, 1996.
  26. STRANGER, R., Dubicki, L. and Krausz, E. A Magneto-Optical Investigation of the Exchange-Coupled Dimer Cs3Mo2Br9.Inorganic Chemistry, 35, 4218-4226, 1996.
  27. McGrady, J.E., STRANGER, R., Bown, M. and Bennett, M.A. Linkage Isomerism in Complexes of ortho-Xylylene: Density Functional Study of the Structure and Bonding in endo- and exo-Ru(PH3)3(o-xylylene). Organometallics, 15, 3109-3114, 1996.
  28. Grey, I.E., Lanyon, M. and STRANGER, R. Structure Characterisation of Sulfate and Oxysulfate Phases Formed During Sulfuric Acid Digestion of Ilmenites. Australian Journal of Chemistry, 49, 801-815, 1996.
  29. STRANGER, R., McGrady, J.E., Arnold, D.P., Lane, I. and Heath G.A. Communication Between Porphyrin Rings in the Butadiyne-Bridged Dimer Ni(OEP)(m-C4)Ni(OEP): a Density Functional Study. Inorganic Chemistry, 35, 7791-7797, 1996.
  30. STRANGER, R., Macgregor, S.A., Lovell, T., McGrady, J.E. and Heath, G.A. A Density Functional Study of the Ground and Excited Spin States of [M2Cl9]3- (M=Mo,W) Face-Shared Dimers: Consequences for Structural Variation in A3M2Cl9 Complexes. Journal of the Chemical Society, Dalton Transactions, 4485-4491, 1996.
  31. STRANGER, R., Nissen, S.C., Mathieson, M.T. and Appleton, T.A. Assignment of Electronic Spectra of the Platinum(III) Dimer Complexes [Pt2(SO4)4(H2O)2]2- and [Pt2(HPO4)4(H2O)2]2-. Inorganic Chemistry, 36, 937-939, 1997.
  32. Cifuentes, M.P., Humphrey, M.G., McGrady, J.E., Smith, P.J., STRANGER, R., Murray, K.S. and Moubaraki, B. High Nuclearity Ruthenium Carbonyl Cluster Chemistry. 5.1 Local Density Functional, Electronic Spectroscopy, Magnetic Susceptibility and Electron Paramagnetic Resonance Studies on (Carbido)decaruthenium Carbonyl Clusters. Journal of the American Chemical Society, 119, 2647-2655, 1997.
  33. Withers, R.L., Lobo, C., Thompson, J.G., Schmid, S. and STRANGER, R. A Modulation Wave Approach to the Structural Characterisation of Three New Cristobalite-Related Sodium Magnesiosilicates. Acta Crystallographica B53, 203-220, 1997.
  34. McGrady, J.E., Lovell, T. and STRANGER, R. Probing the Balance between Localization and Delocalization of the Metal-Based Electrons in Face-Shared Bioctahedral Complexes. Inorganic Chemistry, 36, 3242-3247, 1997.
  35. STRANGER, R., McMahon, K.L., Gahan, L.R., Bruce, J.I. and Hambley, T.W. Spin-Orbit Mixing and Nephelauxetic Effects in the Electronic Spectra of Nickel(II) Encapsulating Complexes involving Nitrogen and Sulfur Donors. Inorganic Chemistry, 36, 3466-3475, 1997.
  36. McGrady, J.E., STRANGER, R. and Lovell, T. Broken-Symmetry and Approximate Spin-Projected Potential Energy Curves for Bimetallic Systems: a Density Functional Study of M2Cl9, M = Cr(III), Mo(III), W(III) and Re(IV). Journal of Physical Chemistry A, 101, 6265-6272, 1997.
  37. McGrady, J.E. and STRANGER, R. Redox-Induced Changes in the Geometry and Electronic Structure of Di-m-Oxo Bridged Manganese Dimers. Journal of the American Chemical Society, 119, 8512-8522, 1997.
  38. McGrady, J.E., Lovell, T., STRANGER, R. and Humphrey, M.G. Bonding of h1-Acetylide Ligands to Electron Rich Ruthenium Centres: can Electron-Deficient Ligands Induce Significant Metal-to-Ligand Back-Bonding? Organometallics, 16, 4004-4011, 1997.
  39. Frankcombe, T.J., STRANGER, R. and Schranz, H.W. The Intermolecular Potential Energy Surface of CO2-Ar and its Effect on Collisional Energy Transfer, Internet Journal of Chemistry, 1, CP1-U25, 1998.


Facilities

  • 12 dual CPU Pentium IV computers (1.7 – 3.0 GHz).
  • Access to ANU Supercomputing facilities.
  • Licenses to run relevant software such as Gaussian and ADF.

International Linkages

Dr T. Lovell (The Scripps Research Institute, La Jolla, USA)
Dr J.E. McGrady (University of York, United Kingdom)
Prof. K. Morokuma (Emory University, Atlanta, USA)
Prof. W.H. Armstrong (Department of Chemistry, Boston College, USA)