A high-resolution XAS study of aqueous Cu(II) in liquid and frozen solutions: pyramidal, polymorphic, and non-centrosymmetric

The Journal of Chemical Physics
Patrick FrankKeith O Hodgson

Abstract

High-resolution EXAFS (k = 18 Å(-1)) and MXAN XAS analyses show that axially elongated square pyramidal [Cu(H2O)5](2+) dominates the structure of Cu(II) in aqueous solution, rather than 6-coordinate JT-octahedral [Cu(H2O)6](2+). Freezing produced a shoulder at 8989.6 eV on the rising XAS edge and an altered EXAFS spectrum, while 1s → 3d transitions remained invariant in energy position and intensity. Core square pyramidal [Cu(H2O)5](2+) also dominates frozen solution. Solvation shells were found at ∼3.6 Å (EXAFS) or ∼3.8 Å (MXAN) in both liquid and frozen phases. However, MXAN analysis revealed that about half the time in liquid solution, [Cu(H2O)5](2+) associates with an axially non-bonding 2.9 Å water molecule. This distant water apparently organizes the solvation shell. When the 2.9 Å water molecule is absent, the second shell is undetectable to MXAN. The two structural arrangements may represent energetic minima of fluxional dissolved aqueous [Cu(H2O)5](2+). The 2.9 Å trans-axial water resolves an apparent conflict of the [Cu(H2O)5](2+) core model with a dissociational exchange mechanism. In frozen solution, [Cu(H2O)5](2+) is associated with either a 3.0 Å axial non-bonded water molecule or an axial ClO4(-) at 3.2 Å. Both s...Continue Reading

References

Mar 1, 1978·European Journal of Biochemistry·J Peisach, W B Mims
Sep 15, 1989·Acta Crystallographica. Section C, Crystal Structure Communications·J C Gallucci, R E Gerkin
Feb 1, 1968·Proceedings of the National Academy of Sciences of the United States of America·B L Vallee, R J Williams
Aug 1, 1994·European Journal of Biochemistry·B G Malmström
Aug 30, 1996·Journal of Molecular Biology·U RydeB O Roos
May 9, 1998·Proceedings of the National Academy of Sciences of the United States of America·A MesserschmidtG W Canters
Dec 1, 1986·Physical Review A: General Physics·C R NatoliS Doniach
Oct 15, 1986·Physical Review. B, Condensed Matter·M BenfattoI Davoli
Oct 1, 1993·Physical Review. B, Condensed Matter·E A Stern
Jun 14, 2000·Biophysical Chemistry·L LiuQ X Guo
Nov 21, 2000·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·H B GrayR J Williams
Nov 21, 2000·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·U RydeK Pierloot
Aug 7, 2001·Journal of Synchrotron Radiation·M Benfatto, S Della Longa
Oct 18, 2003·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Christian F Schwenk, Bernd M Rode
Mar 25, 2004·Journal of the American Chemical Society·Jochen BlumbergerMichiel Sprik
Jul 21, 2004·Journal of Synchrotron Radiation·A MichalowiczG Vlaic
Jun 9, 2005·Chemical Reviews·David T Richens
Sep 29, 2005·Physical Chemistry Chemical Physics : PCCP·Sami AmiraKersti Hermansson
Feb 18, 2006·The Journal of Chemical Physics·Jesús ChaboyEnrique Sánchez Marcos
May 26, 2007·The Journal of Chemical Physics·Takuro IinoHiroshi Sekiya
Jun 1, 2007·The Journal of Physical Chemistry. a·Bridgette J DuncombeAnthony J Stace
Sep 4, 2008·The Journal of Physical Chemistry. a·Vyacheslav S BryantsevWilliam A Goddard
Aug 5, 2009·Photosynthesis Research·Junko Yano, Vittal K Yachandra
Jul 27, 2010·Physical Chemistry Chemical Physics : PCCP·Xiandong LiuRucheng Wang
Aug 22, 2012·Angewandte Chemie·Susana Gómez-SalcesFernando Rodríguez

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Citations

Oct 3, 2015·The Journal of Chemical Physics·G La PennaF Stellato
May 20, 2016·The Journal of Physical Chemistry. a·Giovanni ChillemiMaurizio Benfatto
Aug 1, 2016·The Journal of Chemical Physics·Matthew AntalekPatrick Frank
Dec 23, 2016·Angewandte Chemie·William B O'DellFlora Meilleur
Apr 28, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Claudio EvangelistiMaurizio Benfatto
Nov 5, 2015·Physical Chemistry Chemical Physics : PCCP·Michael T RuggieroTimothy M Korter
Oct 21, 2017·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Derek B RiceTimothy A Jackson
Jun 2, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Tyler M OzvatJoseph M Zadrozny
Jun 17, 2020·Physical Chemistry Chemical Physics : PCCP·Renat NazmutdinovWolfgang Schmickler
Jun 6, 2018·The Journal of Chemical Physics·Patrick FrankMunzarin Qayyum
Mar 5, 2021·Physical Chemistry Chemical Physics : PCCP·Tahmin LaisGopinathan Sankar
Nov 3, 2020·Journal of the American Chemical Society·Ryan D McGillicuddyJarad A Mason
May 24, 2019·Journal of the American Chemical Society·Jian ZhengJohannes A Lercher
Aug 29, 2017·The Journal of Physical Chemistry. B·Akshaya K Das, Markus Meuwly
Jul 3, 2020·Inorganic Chemistry·Ingmar PerssonKajsa G V Sigfridsson Clauss
Apr 1, 2020·The Journal of Physical Chemistry. B·Guoxi RenXiaosong Liu
Sep 22, 2021·The Journal of Physical Chemistry. B·Patrick Frank, Maurizio Benfatto

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