Synthesis, Thermal, Structural Analyses and Photoluminescent Properties of a New Family of Malonate-containing Lanthanide(III) Coordination Polymers

Sajjad Hussain (Corresponding Author), Xuenian Chen, William T. A. Harrison, Saeed Ahmad, Mark R. J. Elsegood, Islam Ullah Khan, Shabbir Muhammad

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Abstract

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.
Original languageEnglish
Article number260
Number of pages16
JournalFrontiers in Chemistry
Volume7
Early online date1 Apr 2019
DOIs
Publication statusPublished - Apr 2019

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Lanthanoid Series Elements
Europium
Polymers
Ions
Optoelectronic devices
Hydrogen
Radiation counters
Geometry
X ray analysis
Magnetic moments
Excited states
Nitrates
Anions
Absorption spectra
Refractive index
Photoluminescence
Hydrogen bonds
Hot Temperature
malonic acid
Single crystals

Keywords

  • Lanthanides
  • Malonate
  • Photoluminescence
  • Crystal structure
  • Optoelectronic Properties
  • Optoelectronic properties
  • photoluminescence
  • MOLECULAR-STRUCTURE
  • COMPLEXES
  • CRYSTAL-STRUCTURES
  • LUMINESCENT PROPERTIES
  • malonate
  • ADSORPTION
  • GADOLINIUM(III)
  • lanthanides
  • RARE-EARTH CARBOXYLATES
  • optoelectronic properties
  • DICARBOXYLATE LIGANDS
  • crystal structure
  • MAGNETIC-PROPERTIES
  • ORGANIC FRAMEWORKS

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis, Thermal, Structural Analyses and Photoluminescent Properties of a New Family of Malonate-containing Lanthanide(III) Coordination Polymers. / Hussain, Sajjad (Corresponding Author); Chen, Xuenian; Harrison, William T. A.; Ahmad, Saeed; Elsegood, Mark R. J.; Khan, Islam Ullah; Muhammad, Shabbir.

In: Frontiers in Chemistry, Vol. 7, 260, 04.2019.

Research output: Contribution to journalArticle

Hussain, Sajjad ; Chen, Xuenian ; Harrison, William T. A. ; Ahmad, Saeed ; Elsegood, Mark R. J. ; Khan, Islam Ullah ; Muhammad, Shabbir. / Synthesis, Thermal, Structural Analyses and Photoluminescent Properties of a New Family of Malonate-containing Lanthanide(III) Coordination Polymers. In: Frontiers in Chemistry. 2019 ; Vol. 7.
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AU - Hussain, Sajjad

AU - Chen, Xuenian

AU - Harrison, William T. A.

AU - Ahmad, Saeed

AU - Elsegood, Mark R. J.

AU - Khan, Islam Ullah

AU - Muhammad, Shabbir

N1 - X.C is grateful for the financial support from the National Natural Science Foundation of China (Grants 21771057). S. H acknowledges Higher Education Commission of Pakistan for IRSIP fellowship and Henan Normal University for postdoctoral support. The authors from KKU also extend their appreciation to Deanship of Scientific Research at King Khalid University for support through Research Groups Project under grant number (R.G.P.2/17/40). We also acknowledge the technical support of Dr. Abdullah for computations.

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N2 - 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.

AB - 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.

KW - Lanthanides

KW - Malonate

KW - Photoluminescence

KW - Crystal structure

KW - Optoelectronic Properties

KW - Optoelectronic properties

KW - photoluminescence

KW - MOLECULAR-STRUCTURE

KW - COMPLEXES

KW - CRYSTAL-STRUCTURES

KW - LUMINESCENT PROPERTIES

KW - malonate

KW - ADSORPTION

KW - GADOLINIUM(III)

KW - lanthanides

KW - RARE-EARTH CARBOXYLATES

KW - optoelectronic properties

KW - DICARBOXYLATE LIGANDS

KW - crystal structure

KW - MAGNETIC-PROPERTIES

KW - ORGANIC FRAMEWORKS

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