Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

Frank, Patrick; Szilagyi, Robert K.; Gramlich, Volker; Hsu, Hua-Fen; Hedman, Britt; Hodgson, Keith O.

doi:10.1021/acs.inorgchem.6b00991

Title: Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

Abstract

Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [M^II(itao)(SO₄)(H₂O)_0,1] (M = Co, Ni, Cu) and [Cu(Me₆tren)(SO₄)] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal–sulfur bond, while the XAS preedge of [Zn(itao)(SO₄)] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO₄)] but not of [Cu(Me₆tren)(SO₄)] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [M^II(SO₄)(H₂O)] (M = Fe, Co, Ni, and Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5–2 eV below the rising sulfur K-edge energy.more »« less

Authors:

^[1]; Szilagyi, Robert K. ^[2]; Gramlich, Volker ^[3]; Hsu, Hua-Fen ^[4]; Hedman, Britt ^[5]; Hodgson, Keith O. ^[6]

Stanford Univ., CA (United States). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Montana State Univ., Bozeman, MT (United States). Dept. of Chemistry and Biochemistry; Momentum Chemical Structure-Function Lab., Budapest (Hungary)
Federal Inst. of Technology, Zurich (Switzerland). ETH-Zentrum, Lab. fuer Kristallographie
National Cheng-Kung Univ., Tainan City (Taiwan). Dept. of Chemistry
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Stanford Univ., CA (United States). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States)

Publication Date:: Mon Jan 09 00:00:00 EST 2017

Research Org.:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); National Institutes of Health (NIH)

OSTI Identifier:: 1353168

Grant/Contract Number:: P41GM103393; AC02-76SF00515

Resource Type:: Accepted Manuscript

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Volume: 56; Journal Issue: 3; Journal ID: ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Frank, Patrick, Szilagyi, Robert K., Gramlich, Volker, Hsu, Hua-Fen, Hedman, Britt, and Hodgson, Keith O. Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer.  United States: N. p., 2017. 
Web.  doi:10.1021/acs.inorgchem.6b00991.

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                    Frank, Patrick, Szilagyi, Robert K., Gramlich, Volker, Hsu, Hua-Fen, Hedman, Britt, & Hodgson, Keith O. Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer.  United States.  https://doi.org/10.1021/acs.inorgchem.6b00991

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                    Frank, Patrick, Szilagyi, Robert K., Gramlich, Volker, Hsu, Hua-Fen, Hedman, Britt, and Hodgson, Keith O. Mon .  
"Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer".  United States.  https://doi.org/10.1021/acs.inorgchem.6b00991.  https://www.osti.gov/servlets/purl/1353168.

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@article{osti_1353168,

  title        = {Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer},

  author       = {Frank, Patrick and Szilagyi, Robert K. and Gramlich, Volker and Hsu, Hua-Fen and Hedman, Britt and Hodgson, Keith O.},

  abstractNote = {Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [MII(itao)(SO4)(H2O)0,1] (M = Co, Ni, Cu) and [Cu(Me6tren)(SO4)] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal–sulfur bond, while the XAS preedge of [Zn(itao)(SO4)] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO4)] but not of [Cu(Me6tren)(SO4)] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [MII(SO4)(H2O)] (M = Fe, Co, Ni, and Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5–2 eV below the rising sulfur K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the copper(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the sulfur and electron hole provides a new mechanism for the counterintuitive appearance of preedge transitions in the XAS spectra of transition-metal oxoanion ligands in the absence of any direct metal–absorber bond. The 2472.1 eV transition is evidence for further radicalization from copper(II), which extends across a hydrogen-bond bridge between sulfate and the itao ligand and involves orbitals at energies below the frontier set. In conclusion, this electronic structure feature provides a direct spectroscopic confirmation of the through-bond electron-transfer mechanism of redox-active metalloproteins.},

  doi          = {10.1021/acs.inorgchem.6b00991},

  journal      = {Inorganic Chemistry},

  number       = 3,

  volume       = 56,

  place        = {United States},

  year         = {Mon Jan 09 00:00:00 EST 2017},

  month        = {Mon Jan 09 00:00:00 EST 2017}

}

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Foster, J. P.; Weinhold, F.
Journal of the American Chemical Society, Vol. 102, Issue 24
DOI: 10.1021/ja00544a007

Sulfur K-Edge X-ray Absorption Spectroscopy as a Probe of Ligand−Metal Bond Covalency: Metal vs Ligand Oxidation in Copper and Nickel Dithiolene Complexes
journal, February 2007

Sarangi, Ritimukta; DeBeer George, Serena; Rudd, Deanne Jackson
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DOI: 10.1021/ja0665949

Kβ Mainline X-ray Emission Spectroscopy as an Experimental Probe of Metal–Ligand Covalency
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Pollock, Christopher J.; Delgado-Jaime, Mario Ulises; Atanasov, Mihail
Journal of the American Chemical Society, Vol. 136, Issue 26
DOI: 10.1021/ja504182n

Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold
journal, March 1998

Casida, Mark E.; Jamorski, Christine; Casida, Kim C.
The Journal of Chemical Physics, Vol. 108, Issue 11
DOI: 10.1063/1.475855

Direct evaluation of electronic coupling mediated by hydrogen bonds: implications for biological electron transfer
journal, September 1995

de Rege, P.; Williams, S.; Therien, M.
Science, Vol. 269, Issue 5229
DOI: 10.1126/science.7660123

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Title: Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

Abstract

Citation Formats

Ligand K-Edge X-ray Absorption Spectroscopy as a Probe of Ligand-Metal Bonding: Charge Donation and Covalency in Copper-Chloride Systems journal, September 1994

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High Covalence in CuSO 4 and the Radicalization of Sulfate: An X-ray Absorption and Density Functional Study journal, December 2004

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Vanadium complexes as models for vanadium species of marine organisms. Synthesis, X-ray structure of oxo(O,O-sulfate)(2,2′:6′,2″-terpyridine)vanadium(IV) hydrate, and density functional geometry optimization analysis of vanadyl complexes journal, January 2000

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[16] SHELXL: High-resolution refinement book, January 1997

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Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint journal, September 1988

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journal, September 1994

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journal, March 1995

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journal, June 2001

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journal, February 2007

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journal, October 2011

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journal, April 2015

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journal, June 2014

Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS ₄ ²⁻ (M = Cr, Mo, W) dianions
journal, January 2014

Polarized-Neutron Study of the Magnetic Moment Density in Antiferromagnetic CuS $O_{4}$
journal, May 1969

High Covalence in CuSO ₄ and the Radicalization of Sulfate: An X-ray Absorption and Density Functional Study
journal, December 2004

Synthesis and x-ray crystal structure of 2,2′,2″-iminotris(acetamidoxime) copper(II) sulphate monohydrate, [CuN(CH2CNH2: NOH)3(SO4)]·H2O
journal, January 1994

Five-Coordinated High-Spin Complexes of Bivalent Cobalt, Nickel, andCopper with Tris(2-dimethylaminoethyl)amine
journal, January 1966

1:1 Metal Complexes of Bivalent Cobalt, Nickel, Copper, Zink, and Cadmium with the Tripodal Ligand tris[2-(dimethylamino)ethyl]amine: Their stabilities and the X-ray crystal structure of its copper(II) complex sulfate
journal, May 1994

Vanadium complexes as models for vanadium species of marine organisms. Synthesis, X-ray structure of oxo(O,O-sulfate)(2,2′:6′,2″-terpyridine)vanadium(IV) hydrate, and density functional geometry optimization analysis of vanadyl complexes
journal, January 2000

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journal, May 1975

A novel thermogravimetric analyser
journal, April 1994

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journal, September 1979

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journal, November 1980

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journal, May 1975

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journal, January 2000

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book, January 1997

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journal, May 1986

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journal, June 2001

Geometrical fitting of experimental XANES spectra by a full multiple-scattering procedure
journal, June 2001

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journal, April 1979

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journal, January 1988

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journal, September 1980

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journal, September 1988

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journal, March 1998

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journal, September 1992

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journal, January 2013

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journal, April 2002

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journal, April 1994

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journal, January 2014

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journal, October 1955

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journal, July 1991

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journal, December 1970

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journal, January 2000

X-ray absorption spectroscopic studies of the blue copper site: metal and ligand K-edge studies to probe the origin of the EPR hyperfine splitting in plastocyanin
journal, January 1993

Spectroscopic and DFT Investigation of [M{HB(3,5- ⁱ ^{Pr ₂ pz) ₃ }(SC ₆ F ₅ )] (M = Mn, Fe, Co, Ni, Cu, and Zn) Model Complexes: Periodic Trends in Metal−Thiolate Bonding}
journal, July 2005

Ligand K-edge X-ray absorption spectroscopic studies: metal-ligand covalency in transition metal tetrathiolates
journal, October 1997

Absolute electronegativity and hardness: application to inorganic chemistry
journal, February 1988

Looking for jarosite on Mars: The low-temperature crystal structure of jarosite
journal, November 2013

Preparation and Structures of K ₃ [V ^III (ox) ₂ ( μ -SO ₄ )] and K ₅ [V ^III (ox) ₂ (SO ₄ ) ₂ ]
journal, September 1993

Investigation of the Electronic Structure of 2Fe−2S Model Complexes and the Rieske Protein Using Ligand K-Edge X-ray Absorption Spectroscopy
journal, March 1999

Covalent Bonding: The Role of Exchange Effects
journal, March 2014

A predictive theoretical model for electron tunneling pathways in proteins
journal, January 1990

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journal, February 2014

Direct evaluation of electronic coupling mediated by hydrogen bonds: implications for biological electron transfer
journal, September 1995

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journal, January 2015

Electron tunneling in azurin: the coupling across a β-sheet
journal, July 1995

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journal, October 1990

Electron transfer in ruthenium-modified proteins
journal, May 1992

Electron Flow through Metalloproteins
journal, November 2013

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journal, January 1977

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journal, November 1980

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journal, August 2001

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journal, July 2005

Experimental and Computational Investigation of Thiolate Alkylation in Ni ^II and Zn ^II Complexes: Role of the Metal on the Sulfur Nucleophilicity
journal, October 2011

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journal, September 1980

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journal, June 2014

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journal, March 1998

Direct evaluation of electronic coupling mediated by hydrogen bonds: implications for biological electron transfer
journal, September 1995