ChemInform Abstract: Rare‐Earth Tetracyanidoborate Salts — Structural Features and Properties Including Luminescence of [RE(H₂O)₈] [B(CN)₄]₃·nH₂O and [RE(H₂O)₇{ϰ¹N‐B(CN)₄}] [B(CN)₄]₂ (RE: Y, Tb, Dy, Ho, Er, Tm, Yb, Lu; n ≤ 3).

Abstract

Crystals of two groups of the new title compounds, which differ in their amount of coordinated and crystallized water molecules are obtained after evaporation of the solvent. [Tb(H2O)8][B(CN)4]3·2.58H2O, [Dy(H2O)8][B(CN)4]3·2.53H2O, and [Y(H 2O)8][B(CN)4]3·2.32H2O crystallize in the monoclinic space group C2/c with Z = 8. After crystallization, a slow structure reorganization with the loss of water molecules finally forms compounds (IVa-h). (IVg) crystalllizes in the monoclinic space group P21/n with Z = 8. The crystal structures are determined by single crystal XRD. Both structures exhibit discrete eight-coordinated Ln 3+ complex cations, as [Ln(H 2O)8] 3+ and [Ln(H2O)7{ 1 N-B(CN)4}] 2+ . Compounds (IVa) and (IVb) show intense green and yellow emission upon excitation at 254 nm. -(FALK, F.; HACKBARTH, L.; LOCHBRUNNER, S.; MARCINIAK, H.; KOECKERLING*, M.; Eur. J. Inorg. Chem. 2016, 4, 469-476, http://dx.

Anhydrous, Homoleptic Lanthanide Frameworks with the Pentafluoroethyltricyanoborate Anion

“…Cyanoborate anions are valuable building blocks, especially for low-viscosity hydrophobic room temperature ionic liquids (RTILs) and as counteranions or ligands in transition metal chemistry. Most coordination compounds of cyanoborate anions have been reported with the tetracyanoborate anion [B­(CN) 4 ] − , − including complexes of main group metals (for example alkali metal cations , ), transition metals (e.g., [Cp 2 ZrCH 3 {B­(CN) 4 }], [Fe­{B­(CN) 4 } 2 (OH 2 ) 2 ]), and rare-earth metals (e.g., [ Ln {B­(CN) 4 }­(OH 2 ) 7 ]­[B­(CN) 4 ] 2 ( Ln = Y, Tb, Dy, Ho, Er, Tm, Yb, Lu)). The aqua complexes can be dehydrated to yield the corresponding homoleptic cyanoborate complexes.…”

“…As outlined, until now, only very few coordination compounds of lanthanides with cyanoborate anions are known. The few structurally characterized complexes contain a lanthanide cation with a substantial number of aqua ligands or solely with water molecules bonded to the metal center. , …”