Please use this identifier to cite or link to this item: https://doi.org/10.1021/acs.inorgchem.1c00581
Title: A Family of Lanthanide Hydroxo Carboxylates with 1D Polymeric Topology and Ln(4) Butterfly Core Exhibits Switchable Supramolecular Arrangement
Authors: Grebenyuk, Dimitry
Zobel, Mirijam
Polentarutti, Maurizio
Ungur, Liviu 
Kendin, Mikhail
Zakharov, Konstantin
Degtyarenko, Pavel
Vasiliev, Alexander
Tsymbarenko, Dmitry
Keywords: Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry
SINGLE-MOLECULE-MAGNET
METAL-ORGANIC FRAMEWORKS
EARTH BASIC NITRATES
CRYSTAL-STRUCTURES
COORDINATION POLYMERS
DYSPROSIUM TRIANGLES
CLUSTER
COMPLEXES
DY-4
RELAXATION
Issue Date: 18-May-2021
Publisher: AMER CHEMICAL SOC
Citation: Grebenyuk, Dimitry, Zobel, Mirijam, Polentarutti, Maurizio, Ungur, Liviu, Kendin, Mikhail, Zakharov, Konstantin, Degtyarenko, Pavel, Vasiliev, Alexander, Tsymbarenko, Dmitry (2021-05-18). A Family of Lanthanide Hydroxo Carboxylates with 1D Polymeric Topology and Ln(4) Butterfly Core Exhibits Switchable Supramolecular Arrangement. INORGANIC CHEMISTRY 60 (11) : 8049-8061. ScholarBank@NUS Repository. https://doi.org/10.1021/acs.inorgchem.1c00581
Abstract: 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.
Source Title: INORGANIC CHEMISTRY
URI: https://scholarbank.nus.edu.sg/handle/10635/228902
ISSN: 00201669
1520510X
DOI: 10.1021/acs.inorgchem.1c00581
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