New Family of Lanthanide-Based
Inorganic–Organic Hybrid Frameworks: Ln<sub>2</sub>(OH)<sub>4</sub>[O<sub>3</sub>S(CH<sub>2</sub>)<sub><i>n</i></sub>SO<sub>3</sub>]·2H<sub>2</sub>O (Ln = La, Ce, Pr, Nd, Sm; <i>n</i> = 3, 4) and Their Derivatives
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Abstract
We report the synthesis and structure characterization
of a new family of lanthanide-based inorganic–organic hybrid
frameworks, Ln<sub>2</sub>(OH)<sub>4</sub>[O<sub>3</sub>S(CH<sub>2</sub>)<sub><i>n</i></sub>SO<sub>3</sub>]·2H<sub>2</sub>O (Ln = La, Ce, Pr, Nd, Sm; <i>n</i> = 3, 4), and their
oxide derivatives. Highly crystallized samples were synthesized by
homogeneous precipitation of Ln<sup>3+</sup> ions from a solution
containing α,ω-organodisulfonate salts promoted by slow
hydrolysis of hexamethylenetetramine. The crystal structure solved
from powder X-ray diffraction data revealed that this material comprises
two-dimensional cationic lanthanide hydroxide {[Ln(OH)<sub>2</sub>(H<sub>2</sub>O)]<sup>+</sup>}<sub>∞</sub> layers, which are
cross-linked by α,ω-organodisulfonate ligands into a three-dimensional
pillared framework. This hybrid framework can be regarded as a derivative
of UCl<sub>3</sub>-type Ln(OH)<sub>3</sub> involving penetration
of organic chains into two {LnO<sub>9</sub>} polyhedra. Substitutional
modification of the lanthanide coordination promotes a 2D arrangement
of the {LnO<sub>9</sub>} polyhedra. A new hybrid oxide, Ln<sub>2</sub>O<sub>2</sub>[O<sub>3</sub>S(CH<sub>2</sub>)<sub><i>n</i></sub>SO<sub>3</sub>], which is supposed to consist of alternating
{[Ln<sub>2</sub>O<sub>2</sub>]<sup>2+</sup>}<sub>∞</sub> layers
and α,ω-organodisulfonate ligands, can be derived from
the hydroxide form upon dehydration/dehydroxylation. These hybrid
frameworks provide new opportunities to engineer the interlayer chemistry
of layered structures and achieve advanced functionalities coupled
with the advantages of lanthanide elements
