A Family of Lanthanide Hydroxo Carboxylates with 1D Polymeric Topology and Ln4 Butterfly Core Exhibits Switchable Supramolecular Arrangement.
Dimitry GrebenyukMirijam ZobelMaurizio PolentaruttiLiviu UngurMikhail KendinKonstantin ZakharovPavel DegtyarenkoAlexander N VasilievDmitry M TsymbarenkoPublished in: Inorganic chemistry (2021)
The unique family of coordination polymers [Ln4(OH)2(piv)10(H2O)2]∞ of 11 lanthanides (Ln = La-Er) has been prepared by a simple solution method based on controlled hydrolysis. The ribbon-like polymeric structure consisting of connected tetranuclear clusters and supported by pivalate ligands and a framework of H-bonds has been revealed by single-crystal X-ray diffraction. While the compounds demonstrate similar PXRD patterns and unit cell parameters, the joint single-crystal XRD and pair distribution function data suggest the significant local structure change along the lanthanide series. The compounds exist as two packing polymorphs (α and β) with similar ribbon geometry, but different supramolecular arrangement of the ribbons. Dehydration of either polymorph does not disturb the tetranuclear core but leads to a translational symmetry loss along the ribbon and a transformation of the 3D-ordered crystal into a 2D-ordered mesostructure. Rehydration of the mesostructure leads to the β polymorph (except La and Ce), allowing the deliberate switching between the polymorphs via dehydration-rehydration evidenced by means of powder X-ray diffraction, pair distribution function analysis, and density functional theory calculations. Ab initio calculations reveal significant magnetic anisotropy of Ln3+ ions with ferro- and antiferromagnetic interactions within tetranuclear [Ln4(OH)2(piv)10(H2O)2] species. Magnetic susceptibility measurements demonstrated antiferromagnetic coupling, slow magnetic relaxation for Dy, Ho, and Er complexes, and field-induced single-chain magnetism for the Dy compound.
Keyphrases
- density functional theory
- single molecule
- molecular dynamics
- energy transfer
- molecularly imprinted
- high resolution
- drug delivery
- single cell
- electron microscopy
- estrogen receptor
- molecular dynamics simulations
- cancer therapy
- water soluble
- magnetic resonance imaging
- solid state
- quantum dots
- cell therapy
- cell proliferation
- high glucose
- diabetic rats
- big data
- electronic health record
- endoplasmic reticulum
- pi k akt
- breast cancer cells
- drug induced
- dna methylation
- artificial intelligence
- stress induced
- transition metal