Synthesis of alkali metal indium thiophosphates containing the discrete anions [In(PS4)(PS5)2]6- and [In(PS4)2(PS5)]6-

Alexander Rothenberger, Collin Morris, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The first discrete anionic indium thiophosphate complexes are reported. The structures of K6[In(PS4)1.5(PS 5)1.5] (1), Rb6[In(PS4)(PS 5)2] (2), and Cs6[In(PS4) 1.5(PS5)1.5] (3) all contain an anionic moiety consisting of octahedrally coordinated indium surrounded by the thiophosphate anions [PS4]3- and the new [PS5]3- ion. The conformation and bonding of the unsymmetric chelate ligand [PS 5]3- to indium give rise to different anions of the general formula [In(PS4)1+x(PS5) 2-x]6- (x = 0, 0.5). The anionic moiety in K 6[In(PS4)1.5(PS5)1.5] (1) consists of cocrystallizing λ-[In(PS4)2(PS 5)]6- and Λλδ-[In(PS 4)(PS5)2]6- anions in a ratio of 1:1 (and their enantiomers). In Rb6[In(PS4)(PS 5)2] (2), no cocrystallizatzion of anions was observed, and only the Λλλ-[In(PS4)(PS5) 2]6- anion (and its enantiomer) is present. Cs 6[In(PS4)1.5(PS5)1.5] (3) shows the same disorder between [PS4]3- and [PS 5]3- ions as in 1. In 3, however, the octahedrally coordinated indium atom and thiophosphate ligands form a Λδδ- [In(PS4)(PS5)2]6- anion cocrystallizing with δ-[In(PS4)2(PS 5)]6-. Additionally, ordered Rb6[In(PS 4)(PS5)2] (2) was characterized by 31P magic angle spinning NMR, Raman spectroscopy, UV-vis solid-state absorption spectroscopy, thermogravimetric analysis, differential thermal analysis, and energy dispersive X-ray analysis.

Original languageEnglish
Pages (from-to)5598-5602
Number of pages5
JournalInorganic Chemistry
Volume49
Issue number12
DOIs
Publication statusPublished - Jun 21 2010

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Alkali Metals
Indium
alkali metals
Anions
indium
anions
synthesis
Enantiomers
enantiomers
Ions
Ligands
ligands
Magic angle spinning
Energy dispersive X ray analysis
Thermal energy
Absorption spectroscopy
thermal energy
chelates
Differential thermal analysis
metal spinning

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Synthesis of alkali metal indium thiophosphates containing the discrete anions [In(PS4)(PS5)2]6- and [In(PS4)2(PS5)]6-. / Rothenberger, Alexander; Morris, Collin; Kanatzidis, Mercouri G.

In: Inorganic Chemistry, Vol. 49, No. 12, 21.06.2010, p. 5598-5602.

Research output: Contribution to journalArticle

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abstract = "The first discrete anionic indium thiophosphate complexes are reported. The structures of K6[In(PS4)1.5(PS 5)1.5] (1), Rb6[In(PS4)(PS 5)2] (2), and Cs6[In(PS4) 1.5(PS5)1.5] (3) all contain an anionic moiety consisting of octahedrally coordinated indium surrounded by the thiophosphate anions [PS4]3- and the new [PS5]3- ion. The conformation and bonding of the unsymmetric chelate ligand [PS 5]3- to indium give rise to different anions of the general formula [In(PS4)1+x(PS5) 2-x]6- (x = 0, 0.5). The anionic moiety in K 6[In(PS4)1.5(PS5)1.5] (1) consists of cocrystallizing λ-[In(PS4)2(PS 5)]6- and Λλδ-[In(PS 4)(PS5)2]6- anions in a ratio of 1:1 (and their enantiomers). In Rb6[In(PS4)(PS 5)2] (2), no cocrystallizatzion of anions was observed, and only the Λλλ-[In(PS4)(PS5) 2]6- anion (and its enantiomer) is present. Cs 6[In(PS4)1.5(PS5)1.5] (3) shows the same disorder between [PS4]3- and [PS 5]3- ions as in 1. In 3, however, the octahedrally coordinated indium atom and thiophosphate ligands form a Λδδ- [In(PS4)(PS5)2]6- anion cocrystallizing with δ-[In(PS4)2(PS 5)]6-. Additionally, ordered Rb6[In(PS 4)(PS5)2] (2) was characterized by 31P magic angle spinning NMR, Raman spectroscopy, UV-vis solid-state absorption spectroscopy, thermogravimetric analysis, differential thermal analysis, and energy dispersive X-ray analysis.",
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N2 - The first discrete anionic indium thiophosphate complexes are reported. The structures of K6[In(PS4)1.5(PS 5)1.5] (1), Rb6[In(PS4)(PS 5)2] (2), and Cs6[In(PS4) 1.5(PS5)1.5] (3) all contain an anionic moiety consisting of octahedrally coordinated indium surrounded by the thiophosphate anions [PS4]3- and the new [PS5]3- ion. The conformation and bonding of the unsymmetric chelate ligand [PS 5]3- to indium give rise to different anions of the general formula [In(PS4)1+x(PS5) 2-x]6- (x = 0, 0.5). The anionic moiety in K 6[In(PS4)1.5(PS5)1.5] (1) consists of cocrystallizing λ-[In(PS4)2(PS 5)]6- and Λλδ-[In(PS 4)(PS5)2]6- anions in a ratio of 1:1 (and their enantiomers). In Rb6[In(PS4)(PS 5)2] (2), no cocrystallizatzion of anions was observed, and only the Λλλ-[In(PS4)(PS5) 2]6- anion (and its enantiomer) is present. Cs 6[In(PS4)1.5(PS5)1.5] (3) shows the same disorder between [PS4]3- and [PS 5]3- ions as in 1. In 3, however, the octahedrally coordinated indium atom and thiophosphate ligands form a Λδδ- [In(PS4)(PS5)2]6- anion cocrystallizing with δ-[In(PS4)2(PS 5)]6-. Additionally, ordered Rb6[In(PS 4)(PS5)2] (2) was characterized by 31P magic angle spinning NMR, Raman spectroscopy, UV-vis solid-state absorption spectroscopy, thermogravimetric analysis, differential thermal analysis, and energy dispersive X-ray analysis.

AB - The first discrete anionic indium thiophosphate complexes are reported. The structures of K6[In(PS4)1.5(PS 5)1.5] (1), Rb6[In(PS4)(PS 5)2] (2), and Cs6[In(PS4) 1.5(PS5)1.5] (3) all contain an anionic moiety consisting of octahedrally coordinated indium surrounded by the thiophosphate anions [PS4]3- and the new [PS5]3- ion. The conformation and bonding of the unsymmetric chelate ligand [PS 5]3- to indium give rise to different anions of the general formula [In(PS4)1+x(PS5) 2-x]6- (x = 0, 0.5). The anionic moiety in K 6[In(PS4)1.5(PS5)1.5] (1) consists of cocrystallizing λ-[In(PS4)2(PS 5)]6- and Λλδ-[In(PS 4)(PS5)2]6- anions in a ratio of 1:1 (and their enantiomers). In Rb6[In(PS4)(PS 5)2] (2), no cocrystallizatzion of anions was observed, and only the Λλλ-[In(PS4)(PS5) 2]6- anion (and its enantiomer) is present. Cs 6[In(PS4)1.5(PS5)1.5] (3) shows the same disorder between [PS4]3- and [PS 5]3- ions as in 1. In 3, however, the octahedrally coordinated indium atom and thiophosphate ligands form a Λδδ- [In(PS4)(PS5)2]6- anion cocrystallizing with δ-[In(PS4)2(PS 5)]6-. Additionally, ordered Rb6[In(PS 4)(PS5)2] (2) was characterized by 31P magic angle spinning NMR, Raman spectroscopy, UV-vis solid-state absorption spectroscopy, thermogravimetric analysis, differential thermal analysis, and energy dispersive X-ray analysis.

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