Volume 2018, Issue 19 p. 1969-1975
Full Paper

Azobis[tetrazolide]-Carbonates of the Lanthanides – Breaking the Gadolinium Break

Danny Müller

Corresponding Author

Danny Müller

Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-AC, 1060 Vienna, Austria

Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-AC, 1060 Vienna, Austria

E-mail: [email protected]

http://www.ias.tuwien.ac.at

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Christian Knoll

Christian Knoll

Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-AC, 1060 Vienna, Austria

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Andrea Herrmann

Andrea Herrmann

Atominstitut, TU Wien, Stadionallee 2, 1020 Vienna, Austria

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Gökcen Savasci

Gökcen Savasci

Theoretical Chemistry Group, University of Munich (LMU), Butenandtstr. 7 (C), 81377 München, Germany

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Jan M. Welch

Jan M. Welch

Atominstitut, TU Wien, Stadionallee 2, 1020 Vienna, Austria

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Werner Artner

Werner Artner

X-ray Center, TU Wien, Getreidemarkt 9, 1060 Vienna, Austria

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Johannes Ofner

Johannes Ofner

Institute of Chemical Technologies and Analytics, TU Wien, Getreidemarkt 9, 1060 Vienna, Austria

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Bernhard Lendl

Bernhard Lendl

Institute of Chemical Technologies and Analytics, TU Wien, Getreidemarkt 9, 1060 Vienna, Austria

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Gerald Giester

Gerald Giester

Department of Mineralogy and Crystallography, University of Vienna, Althanstraße 14 (UZA 2), 1090 Vienna, Austria

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Peter Weinberger

Peter Weinberger

Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-AC, 1060 Vienna, Austria

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Georg Steinhauser

Corresponding Author

Georg Steinhauser

Institute of Radiation Protection and Radioecology, Leibniz Universität Hannover, Herrenhäuser Str. 2, 30419 Hannover, Germany

Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-AC, 1060 Vienna, Austria

E-mail: [email protected]

http://www.ias.tuwien.ac.at

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First published: 17 February 2018
Citations: 8

Graphical Abstract

Rare earth element (REE) compounds with tetrazole-derivative anions have been prime examples of the “gadolinium break” by showing a structural discontinuity along the series after Gd. Here we present a series of REE compounds with azobis[tetrazolide] ligands that exhibit isotypic crystal structures (from Y and La to Yb) by introducing a bridging carbonato ligand. They hence “overcome” the Gd break.

Abstract

A series of rare earth element (REE) mixed-anion 5,5′-azobis(1H-tetrazol-1-ide)-carbonate ([REE2(ZT)2CO3(H2O)10]·2H2O; REE = lanthanides plus yttrium) coordination compounds were synthesized, characterized, and analyzed. Syntheses by simple metathesis reactions under a CO2 atmosphere were carried out at ambient (La–Gd and Ho) and elevated pressures (55 bar; Tb, Dy, Er, Tm, Yb, and Y). The resulting crystalline materials were characterized principally by single-crystal X-ray diffraction and vibrational spectroscopy (infrared and Raman). All materials are structurally isotypic, crystallizing in the space group C2/c and show nearly identical spectroscopic properties for all the elements investigated. Cell parameters, bond lengths, and bond angles differ marginally, revealing only a slight variation coinciding with the lanthanide (Ln) contraction, that is, the change in the ionic radii of the trivalent rare earth elements. The herein reported series of rare earth element azobis[tetrazolide]-carbonates represents a remarkable exception as they are a series of isotypic REE coordination compounds with tetrazolide-derived ligands unaffected by the “gadolinium break”.