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A new series of 3D lanthanide phenoxycarboxylates: synthesis, crystal structure, magnetism and photoluminescence studies

A new series of 3D lanthanide phenoxycarboxylates: synthesis, crystal structure, magnetism and... A new series of 3D lanthanide (Ln) frameworks has been synthesized with the general formula [{Ln(L)(H2O)}·H2O]n (where Ln = La(1), Tb(2) and Dy(3); L = (HO)OC6H2(CH2COO)2; H3L = 2,5-dihydroxy-1,4-benzenediacetic acid = DHBDA). All the crystals were analyzed by single crystal X-ray diffraction. The Ln ions are octa-coordinated having the square antiprism geometry with the D4d symmetry and connected along the crystallographic a-axis forming a zigzag chain. These chains are further connected by the ligands in three-dimensional crystallographic space. Compounds 2 and 3 were subjected to variable temperature magnetic susceptibility measurements and photoluminescence studies. Magnetic studies reveal that compound 2 possesses antiferromagnetic coupling whereas compound 3 shows ferromagnetic interaction at temperatures above ca. 40 K. The emission spectra of compounds 2 and 3 combine the intra-4f emission of the Ln ions with that of the ligand, depending on the selected temperature, pointing out that the energy transfer processes are thermally activated. In addition, compound 2 presented an invariant 5D4 lifetime behaviour at temperatures between 15 and 300 K. Theoretical analysis showed that the long-lived lifetimes of the free ligand's excited states and the intramolecular energy transfer rate invariability are responsible for such abnormal behaviour. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png CrystEngComm Royal Society of Chemistry

A new series of 3D lanthanide phenoxycarboxylates: synthesis, crystal structure, magnetism and photoluminescence studies

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References (70)

Publisher
Royal Society of Chemistry
Copyright
This journal is © The Royal Society of Chemistry
ISSN
1466-8033
eISSN
1466-8033
DOI
10.1039/d1ce00228g
Publisher site
See Article on Publisher Site

Abstract

A new series of 3D lanthanide (Ln) frameworks has been synthesized with the general formula [{Ln(L)(H2O)}·H2O]n (where Ln = La(1), Tb(2) and Dy(3); L = (HO)OC6H2(CH2COO)2; H3L = 2,5-dihydroxy-1,4-benzenediacetic acid = DHBDA). All the crystals were analyzed by single crystal X-ray diffraction. The Ln ions are octa-coordinated having the square antiprism geometry with the D4d symmetry and connected along the crystallographic a-axis forming a zigzag chain. These chains are further connected by the ligands in three-dimensional crystallographic space. Compounds 2 and 3 were subjected to variable temperature magnetic susceptibility measurements and photoluminescence studies. Magnetic studies reveal that compound 2 possesses antiferromagnetic coupling whereas compound 3 shows ferromagnetic interaction at temperatures above ca. 40 K. The emission spectra of compounds 2 and 3 combine the intra-4f emission of the Ln ions with that of the ligand, depending on the selected temperature, pointing out that the energy transfer processes are thermally activated. In addition, compound 2 presented an invariant 5D4 lifetime behaviour at temperatures between 15 and 300 K. Theoretical analysis showed that the long-lived lifetimes of the free ligand's excited states and the intramolecular energy transfer rate invariability are responsible for such abnormal behaviour.

Journal

CrystEngComm – Royal Society of Chemistry

Published: Jun 15, 2021

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