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Synthesis, thermal, structural analyses and photoluminescent properties of a new family of malonate-containing lanthanide(III) coordination polymers

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posted on 10.04.2019, 09:24 authored by Sajjad Hussain, Xuenian Chen, William T. Harrison, Saeed Ahmad, Mark ElsegoodMark Elsegood, Islam U. Khan, Shabbir Muhammad
Five new Lanthanide(III) complexes of malonic acid (HOOC-CH2-COOH); {[Gd(C3H2O4)(H2O)4]•NO3}n (1), {[Tb(C3H2O4)(H2O)4]•NO3}n (2),{[Ho(C3H2O4)(H2O)4]•NO3}n (3), [Er(C3H2O4)(C3H3O4)(H2O)2]n (4) and {[Eu2(C3H2O4)2(C3H3O4)2(H2O)6]•4H2O}n (5) are synthesized and characterized by elemental, infrared spectral and thermal analyses. The structures of compounds 1-5 are determined by single crystal X-ray diffraction technique. The X-ray analysis reveals that compounds 1, 2 and 3 are isostructural and crystallized in the orthorhombic space group Pmn21. The lanthanide(III) ions are coordinated by four carboxylate and four water oxygen atoms adopting a distorted square antiprism geometry. The LnO8 square antiprisms are linked into infinite layers by malonate (C3H2O42–) dianions sandwiching sheets of nitrate counter ions. Compound 4 contains ErO8 square antiprisms linked into a two-dimensional network by hydrogen malonate (C3H3O4–) anions and malonate dianions. The europium complex, 5 is dinuclear having the two europium(III) ions (Eu1 and Eu2) bridged by carboxylate groups of hydrogen malonate ligands. The europium ions in 5 are nine-coordinate and exhibit a distorted monocapped square antiprism geometry. All the structures are consolidated by O–H∙∙∙O hydrogen bonds. The photoluminescence spectra of 1-5 exhibit characteristics emission in the visible region. The IR spectra and thermal data are consistent with the structural results. The room-temperature effective magnetic moments for 1–4 are in good agreement with those expected for the free ions, while the data for 5 indicates that low-lying excited states contribute to the observed moment. The compound 1 was further subjected to quantum computational calculations to explore its optoelectronic properties including; density of states (DOS), dielectric function, refractive index, extinction coefficient and absorption spectrum, to highlight the possible applications of such materials in the optoelectronics.

History

School

  • Science

Department

  • Chemistry

Published in

Frontiers in Chemistry

Citation

HUSSAIN, S. ... et al, 2019. Synthesis, thermal, structural analyses and photoluminescent properties of a new family of malonate-containing lanthanide(III) coordination polymers. Frontiers in Chemistry, 7, Article 260.

Publisher

Frontiers Media © The Authors

Version

VoR (Version of Record)

Publisher statement

This work is made available according to the conditions of the Creative Commons Attribution 4.0 International (CC BY 4.0) licence. Full details of this licence are available at: http://creativecommons.org/licenses/ by/4.0/

Acceptance date

01/04/2019

Publication date

2019-04-30

Notes

This is an Open Access article. It is published by Frontiers Media under the Creative Commons Attribution 4.0 International Licence (CC BY). Full details of this licence are available at: https://creativecommons.org/licenses/by/4.0/. This paper will be made available once it has been published.

ISSN

2296-2646

Language

en