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On the Scope of XPS as Sensor in Coordination Chemistry of Transition Metal Hexacyanometallates
Author(s) -
Cano Arely,
RodríguezHernández Joelis,
Reguera Leslie,
RodríguezCastellón Enrique,
Reguera Edilso
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201801556
Subject(s) - chemistry , x ray photoelectron spectroscopy , transition metal , coordination number , crystallography , coordination complex , octahedron , metal , metal l edge , ion , metal k edge , crystal structure , nuclear magnetic resonance , biochemistry , physics , organic chemistry , catalysis
This study reports an evaluation on the scope of X‐ray photoelectron spectroscopy (XPS) to obtain information for the coordination chemistry of transition metal (T n ) hexacyanometallates, T x A z [M m (CN) 6 ] y where nx + z = y (6 – m ), A is an alkaline charge‐compensating cation, and M m is a transition metal with a maximum of 6 electrons in its n d orbitals. XPS provides an elegant picture on the role of the CN π‐back bonding effect to determine the charge density on the N atom and, from this fact, on its coordination to transition metal ions to form coordination polymers. XPS appears to be able to discriminate between octahedral and tetrahedral coordination for the outer metal (T) to the N end of CN ligands, particularly when the XPS peak and the Auger lines are combined. A similar performance was observed when this spectroscopic technique is used to identify when the CN ligand is found with linear and bifurcated coordination mode to the metal linked at its N end. These last two structural features are relevant in the coordination of metal hexacyanometallates and determine their physical and functional properties. The results obtained from XPS data were correlated with the a priori information from IR spectra and the reported crystal structures for all the samples under study.