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Structural Evolution in a Series of Isomorphous Rare Earth Compounds as Response of Lanthanide Contraction

Authors :
Hans Reuter
Marcel Böltken
Maik Horstmann
Markus Haase
Source :
Crystals, Vol 13, Iss 7, p 1043 (2023)
Publication Year :
2023
Publisher :
MDPI AG, 2023.

Abstract

The structural parameters of the rare-earth diacetate halide trihydrates, RE(OAc)2Hal·3H2O with RE = Ce − (Pm) − Lu and Hal = Cl, Br, have been determined by low temperature, high-resolution SCXRD in order to examine the effect of lanthanide contraction on the coordination geometry in this series of isomorphous compounds consisting of cationic, acetate-bridged, non-linear, one-dimensional coordination polymers of composition [RE(H2O)3(OAc)2]+ and laterally hydrogen bonded halide ions, Hal−. Although the shrinkage of the unit cell volume follows lanthanide contraction very well over the complete range of investigated RE elements, many other parameters (i.e., lattice constants, angles and distances in the RE··· RE alignment, RE-O bond lengths, etc.) exhibit a more complex response on lanthanide contraction often expressed by sigmoid curves that can be ascribed to a continuous transition from CN9 (RE = Ce) to CN8 (RE = Lu) as one acetate group loses the chelate function, an effect accompanied by significant structural changes of the carboxylate group. Therefore, data are best analyzed by use of two subsets represented by the two different structure types of Ce and Lu, the structural features of which change with decreasing/increasing the size of RE3+, up to the borderline between both subsets.

Details

Language :
English
ISSN :
20734352
Volume :
13
Issue :
7
Database :
Directory of Open Access Journals
Journal :
Crystals
Publication Type :
Academic Journal
Accession number :
edsdoj.befcb6ab8bb14c9695e9bac116ebaf9d
Document Type :
article
Full Text :
https://doi.org/10.3390/cryst13071043