TY - JOUR

T1 - Azobis[tetrazolide]-Carbonates of the Lanthanides

T2 - Breaking the Gadolinium Break

AU - Müller, Danny

AU - Knoll, Christian

AU - Herrmann, Andrea

AU - Savasci, Gökcen

AU - Welch, Jan M.

AU - Artner, Werner

AU - Ofner, Johannes

AU - Lendl, Bernhard

AU - Giester, Gerald

AU - Weinberger, Peter

AU - Steinhauser, Georg

N1 - Funding information: We acknowledge financial support of the Austrian Science Fund (FWF-Der Wissenschaftsfond) project P24955-N28. This work was performed in the framework of the Corporation in Science and Technology (COST) action CM1305 “Explicit Control Over Spin-states in Technology and Biochemistry (ECOSTBio). The X-ray center (XRC) of the TU Wien provided access to the powder X-ray diffractometer.

PY - 2018/5/24

Y1 - 2018/5/24

N2 - 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”.

AB - 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”.

KW - Carbon dioxide fixation

KW - Coordination chemistry

KW - Gadolinium break

KW - Isotypic structures

KW - Lanthanides

KW - Ligand effects

UR - http://www.scopus.com/inward/record.url?scp=85045318022&partnerID=8YFLogxK

U2 - 10.1002/ejic.201800218

DO - 10.1002/ejic.201800218

M3 - Article

AN - SCOPUS:85045318022

VL - 2018

SP - 1969

EP - 1975

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 19

ER -