1. Created by Karen McFarlane Holman, Willamette University (kholman@willamette.edu) and posted on VIPEr (www.ionicviper.org) on June 27, 2013. Copyright Karen McFarlane Holman 2013. This work is licensed under the Creative Commons Attribution-NonCommerical-ShareAlike 3.0 Unported License. To view a copy of this license visit http://creativecommons.org/about/license/.kholman@willamette.eduwww.ionicviper.org http://creativecommons.org/about/license/ XAS & LFT: X-ray absorption spectroscopy (XAS) as a tool to investigate ligand field theory

2. For coordination compounds, how does one measure… Magnitude of d-d splitting? Magnitude of charge transfer (CT) transitions? MO energy levels? Extent of M-L orbital overlap? Electronic environment (oxidation state, Z eff )?

3. For coordination compounds, how does one measure… Magnitude of d-d splitting? Magnitude of charge transfer (CT) transitions? MO energy levels? Extent of M-L orbital overlap? Electronic environment (oxidation state, Z eff )? X-ray absorption spectroscopy (XAS)can be used to determine all of these things simultaneously!

4. What is XAS? X-ray High energy photons eject core e - s (1s, 2s, etc.) Absorption Spectroscopy Scan over a spectrum, measure absorbance of photons that eject e - s or fluorescence of photons emitted when valence e - s relax into holes 1s h h 3d 4p Elemental Fe:

5. Just another spectrometer Stanford Synchrotron Radiation Lightsource Beamline 11-2 Ion Chamber 0 Ion Chamber 1 Ion Chamber 2 Sample Detector standard Slits Although you do need a special photon source…

6. X-rays emerge from the source: A particle accelerator called a synchrotron Dave, an undergraduate student from Willamette University, collects data at the Advanced Light Source, Lawrence Berkeley National Laboratory.

7. X-rays reach the sample chamber Look through The leaded glass window:

8. Ligand 1s Metal d manifold h h Sample Backside of Detector Inside the sample chamber 5d 5 metal complex, D 4h symmetry

9. Synchrotron The light source for intense, coherent X-rays used for XAS Advanced Photon Source The Advanced Light Source

10. Origin of each part of an X-ray absorption spectrum Pre-edge, K-edge (XANES), and EXAFS regions TransmissionAbsorption/fluorescence Thank you to Chris Kim, Chapman U., for providing most of this slide!

11. Some definitions… XANES: X-ray absorption near-edge structure is the region of the XAS spectrum leading up to and at the K-edge of an element. K-edge: The energy required to eject a 1s electron (akin to ionization energy, but for core electrons). Pre-edge features: Peaks in the XANES spectrum corresponding to electronic transitions from core electrons to bound states that occur slightly below the K-edge energy.

12. Features of XAS Example: Ru(bpy) 3 2+

13. Element Specific: Edges energies well resolved for different elements

14. Element Specific Ru

15. Element Specific N

16. C

17. Oxidation State: K-edge energies shift when an element is oxidized or reduced or Z eff changes

18. Bond lengths: Can be determined via EXAFS (another type of XAS experiment not discussed here)

19. Identify Ligand: Useful for bioinorganic systems or when identity of ligand is ambiguous

20. Orbital mixing Extent of M-L overlap can be determined from spectral features in the pre-edge region

21. Coordination number/symmetry: Can be determined from XANES and EXAFS

22. In situ experiments are possible: Extremely useful for dilute samples such as probing a metal catalytic site in an enzyme; Often non-destructive

23. Adapted from I.J. Pickering, R.C. Prince, T. Divers, G.N. George, FEBS Letters 1998, 441, 11-14. Sulfur K-edge XANES Spectra SO 4 2- SO 3 2- RSH RSSR MS x 2460 2470 2480 2490 Energy (eV) Normalized Absorbance EXAMPLE 1:

24. Adapted from I.J. Pickering, R.C. Prince, T. Divers, G.N. George, FEBS Letters 1998, 441, 11-14. Sulfur K-edge XANES Spectra SO 4 2- SO 3 2- RSH RSSR MS x 2460 2470 2480 2490 Energy (eV) Normalized Absorbance K-edge = 2480 eV S 6+

25. Adapted from I.J. Pickering, R.C. Prince, T. Divers, G.N. George, FEBS Letters 1998, 441, 11-14. Sulfur K-edge XANES Spectra SO 4 2- SO 3 2- RSH RSSR MS x 2460 2470 2480 2490 Energy (eV) Normalized Absorbance K-edge = 2475 eV S 4+

26. Adapted from I.J. Pickering, R.C. Prince, T. Divers, G.N. George, FEBS Letters 1998, 441, 11-14. Sulfur K-edge XANES Spectra SO 4 2- SO 3 2- RSH RSSR MS x 2460 2470 2480 2490 Energy (eV) Normalized Absorbance

27. Adapted from I.J. Pickering, R.C. Prince, T. Divers, G.N. George, FEBS Letters 1998, 441, 11-14. Sulfur K-edge XANES Spectra SO 4 2- SO 3 2- RSH RSSR MS x 2460 2470 2480 2490 Energy (eV) Normalized Absorbance 2GSH GSSG -2H +, -2e - +2H +, +2e -

28. Adapted from I.J. Pickering, R.C. Prince, T. Divers, G.N. George, FEBS Letters 1998, 441, 11-14. Sulfur K-edge XANES Spectra SO 4 2- SO 3 2- RSH RSSR MS x 2460 2470 2480 2490 Energy (eV) Normalized Absorbance

29. Adapted from I.J. Pickering, R.C. Prince, T. Divers, G.N. George, FEBS Letters 1998, 441, 11-14. Sulfur K-edge XANES Spectra SO 4 2- SO 3 2- RSH RSSR MS x 2460 2470 2480 2490 Energy (eV) Normalized Absorbance K-edge

30. Adapted from I.J. Pickering, R.C. Prince, T. Divers, G.N. George, FEBS Letters 1998, 441, 11-14. Sulfur K-edge XANES Spectra SO 4 2- SO 3 2- RSH RSSR MS x 2460 2470 2480 2490 Energy (eV) Normalized Absorbance K-edge

31. Adapted from I.J. Pickering, R.C. Prince, T. Divers, G.N. George, FEBS Letters 1998, 441, 11-14. Sulfur K-edge XANES Spectra SO 4 2- SO 3 2- RSH RSSR MS x 2460 2470 2480 2490 Energy (eV) Normalized Absorbance Pre-edge

32. Adapted from I.J. Pickering, R.C. Prince, T. Divers, G.N. George, FEBS Letters 1998, 441, 11-14. Sulfur K-edge XANES Spectra SO 4 2- SO 3 2- RSH RSSR MS x 2460 2470 2480 2490 Energy (eV) Normalized Absorbance Pre-edge Due to M-L bonding

33. Adapted from B. Hedman, K.O. Hodgson, E.I. Solomon J. Am. Chem. Soc. 1990, 112, 1643-1645. Chlorine K-edge XANES Spectra in MCl 4 2- 2820 2830 2840 Energy (eV) Normalized Absorbance CuCl 4 2- D 4h CuCl 4 2- D 2d ZnCl 4 2- D 2d EXAMPLE 2:

34. Adapted from B. Hedman, K.O. Hodgson, E.I. Solomon J. Am. Chem. Soc. 1990, 112, 1643-1645. Chlorine K-edge XANES Spectra in MCl 4 2- 2820 2830 2840 Energy (eV) Normalized Absorbance CuCl 4 2- D 4h CuCl 4 2- D 2d ZnCl 4 2- D 2d

35. Adapted from B. Hedman, K.O. Hodgson, E.I. Solomon J. Am. Chem. Soc. 1990, 112, 1643-1645. Chlorine K-edge XANES Spectra in MCl 4 2- 2820 2830 2840 Energy (eV) Normalized Absorbance CuCl 4 2- D 4h CuCl 4 2- D 2d ZnCl 4 2- D 2d Cl 1s Cl 3p Cu 3d x2-y2 continuum

36. Adapted from B. Hedman, K.O. Hodgson, E.I. Solomon J. Am. Chem. Soc. 1990, 112, 1643-1645. Chlorine K-edge XANES Spectra in MCl 4 2- 2820 2830 2840 Energy (eV) Normalized Absorbance CuCl 4 2- D 4h CuCl 4 2- D 2d ZnCl 4 2- D 2d Cl 1s Cl 3p Cu 3d x2-y2 continuum

37. Adapted from B. Hedman, K.O. Hodgson, E.I. Solomon J. Am. Chem. Soc. 1990, 112, 1643-1645. Chlorine K-edge XANES Spectra in MCl 4 2- 2820 2830 2840 Energy (eV) Normalized Absorbance CuCl 4 2- D 4h CuCl 4 2- D 2d ZnCl 4 2- D 2d Cl 1s Cl 3p Cu 3d x2-y2 continuum K-edge energy: oxidation state, local environment

38. Adapted from B. Hedman, K.O. Hodgson, E.I. Solomon J. Am. Chem. Soc. 1990, 112, 1643-1645. Chlorine K-edge XANES Spectra in MCl 4 2- 2820 2830 2840 Energy (eV) Normalized Absorbance CuCl 4 2- D 4h CuCl 4 2- D 2d ZnCl 4 2- D 2d Cl 1s Cl 3p Cu 3d x2-y2 continuum

39. Adapted from B. Hedman, K.O. Hodgson, E.I. Solomon J. Am. Chem. Soc. 1990, 112, 1643-1645. Chlorine K-edge XANES Spectra in MCl 4 2- 2820 2830 2840 Energy (eV) Normalized Absorbance CuCl 4 2- D 4h CuCl 4 2- D 2d ZnCl 4 2- D 2d Cl 1s Cl 3p Cu 3d x2-y2 continuum

40. Adapted from B. Hedman, K.O. Hodgson, E.I. Solomon J. Am. Chem. Soc. 1990, 112, 1643-1645. Chlorine K-edge XANES Spectra in MCl 4 2- 2820 2830 2840 Energy (eV) Normalized Absorbance CuCl 4 2- D 4h CuCl 4 2- D 2d ZnCl 4 2- D 2d Cl 1s Cl 3p Cu 3d x2-y2 continuum Pre-edge Energy: MO energy levels

41. Adapted from B. Hedman, K.O. Hodgson, E.I. Solomon J. Am. Chem. Soc. 1990, 112, 1643-1645. Chlorine K-edge XANES Spectra in MCl 4 2- 2820 2830 2840 Energy (eV) Normalized Absorbance CuCl 4 2- D 4h CuCl 4 2- D 2d ZnCl 4 2- D 2d Cl 1s Cl 3p Cu 3d x2-y2 continuum Pre-edge peak area: Orbital overlap (covalency of M-L bond)

42. Adapted from B. Hedman, K.O. Hodgson, E.I. Solomon J. Am. Chem. Soc. 1990, 112, 1643-1645. Chlorine K-edge XANES Spectra in MCl 4 2- 2820 2830 2840 Energy (eV) Normalized Absorbance CuCl 4 2- D 4h CuCl 4 2- D 2d ZnCl 4 2- D 2d Cl 1s Cl 3p Zn 3d x2-y2 continuum

43. Adapted from B. Hedman, K.O. Hodgson, E.I. Solomon J. Am. Chem. Soc. 1990, 112, 1643-1645. Chlorine K-edge XANES Spectra in MCl 4 2- 2820 2830 2840 Energy (eV) Normalized Absorbance CuCl 4 2- D 4h CuCl 4 2- D 2d ZnCl 4 2- D 2d Cl 1s Cl 3p Zn 3d x2-y2 continuum No Pre-edge Feature

44. e g a 1g t 1u e g e g * a 1g a 1g * t 1u t 1u * t 1u a 1g e g +t 2g 4d 5s 5p 6 L (LGOs) M LMCT UV-Vis t 2g nb ML 6 The Full Picture: LMCT transitions are not always measureable with UV-Vis (instrument limitations)

45. The Full Picture: Energy levels of various valence shell MOs are measurable via XANES. Couple with Density Functional Theory (DFT) calculations.

46. The Full Picture: Energy levels of various valence shell MOs are measurable via XANES. Couple with Density Functional Theory (DFT) calculations. Plus, you can determine Z eff, oxidation state, and extent of M-L overlap. XANES rules!