Oxo-centered regular octahedral lanthanide clusters

Ligand-controlled self-assembly of polynuclear lanthanide–oxo/hydroxo complexes: from synthetic serendipity to rational supramolecular design

“…In fact, the octahedral core appears to be another common structural motif in lanthanide oxo-hydroxides, as demonstrated by our group 42 and others. 43,45 Its presence has also been recognized in a polymeric cyanidebridged lanthanide-transition metal complex reported by Shore and coworkers. 47 In stark contrast to the extensive chemistry of the closely related lanthanide oxo-alkoxides, 16a,48 the closely related chemistry of lanthanide oxo-hydroxides has essentially been unexplored.…”

“…However, the isolation of the tyrosine-free complex, [Er 6 (m 6 -O)(m 3 -OH) 8 (NO 3 ) 6 (H 2 O) 12 ](NO 3 ) 2 , from a hydrolytic reaction involving Er(NO 3 ) 3 , tyrosine and NaOH was unexpected and intriguing. Admittedly, this and related hexanuclear complexes 43,45 are structurally drastically different from the cubane-like tetranuclear species. But are tyrosine or any organic ligands really necessary in controlling the hydrolysis of the lanthanide ions?…”

Synthesis and Structural Characterization of Nonanuclear Lanthanide Complexes

“…As prominent precursors in sol−gel processes, lanthanide oxo−alkoxide complexes have been studied intensively, 10b, whereas reports on polynuclear oxo−hydroxo lanthanide clusters are rather limited. Hexanuclear complexes containing a [Ln 6 (μ 6 -O)(μ 3 -OH) 8 ] 8+ core were synthesized via the direct hydrolysis of lanthanide nitrates and perchlorates . Hubert-Pfalzgraf et al reported the synthesis of a nonanuclear [Na(EtOH) 6 ][Y 9 O 2 (OH) 8 (AAA) 16 ] in the presence of β-diketonate allyl acetoacetate ligand under an inert atmosphere .…”

Syntheses and crystal structures of rare earth basic nitrates hydrates

“…While l-tyrosine-controlled hydrolysis of Ln(ClO 4 ) 3 in the presence of halide ions (Ln = Eu, Nd, Gd, Pr) yielded pentadecanuclear Ln clusters with a halide anion in the middle of the cluster, the same procedure with Er(NO 3 ) 3 led to a formation of a well known octahedral cluster [Ln 6 ( 6 -O)( 3 -OH) 8 (H 2 O) 12 (2)(3) 6 ] [1a,c,2,3]. A hydrolysis of Nd and Gd perchlorates supported by l-serine led to a formation of new hydroxoclusters [Ln 6 ( 6 -O)( 3 -OH) 8 (H 2 O) 24 ] [4]. However, if the hydrolysis is performed without the presence of l-serine, the respective Gd cluster contains perchlorate anions in the coordination sphere of Gd with the formula [Gd 6 ( 6 -O)( 3 -OH) 8 (H 2 O) 20 ( 2 -ClO 4 ) 2 ] [5].…”