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

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

Content Provider	PubMed Central
Author	Frank, Patrick Benfatto, Maurizio Qayyam, Munzarin Hedman, Britt Hodgson, Keith O.
Copyright Year	2015
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 structures are again of approximately equal presence. When the axial ClO4 − is present, Cu(II) is ∼0.5 Å above the mean O4 plane. This study establishes [Cu(H2O)5]2+ as the dominant core structure for Cu(II) in water solution, and is the first to both empirically resolve multiple extended solution structures for fluxional [Cu(H2O)5]2+ and to provide direct evidence for second shell dynamics.
Related Links	http://dx.doi.org/10.1063/1.4908266
Starting Page	84310
File Format	PDF
ISSN	00219606
e-ISSN	10897690
Journal	The Journal of Chemical Physics
Issue Number	8
Volume Number	142
Language	English
Publisher	AIP Publishing LLC
Publisher Date	2015-02-28
Access Restriction	Open
Rights Holder	AIP Publishing LLC
Subject Keyword	Physical and Theoretical Chemistry Physics and Astronomy(all) Research in Higher Education
Content Type	Text
Resource Type	Article
Subject	Physics and Astronomy Medicine Physical and Theoretical Chemistry

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