Soft-hard acid-base interactions

Probing coordination preferences of sulfur and selenium in mixed chalcophosphates in the family APbPS 4-xSex (A=K, Rb, Cs; x=0-4)

Alexander Rothenberger, Collin Morris, Hsien Hau Wang, Duck Young Chung, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The synthesis and structures of the three new compounds, KPbPSL 1.84Se2.16 (1), RbPbPSL1.56Se2.43 (2), and CsPbPS3.46Se0.54 (3), are reported. The solid state structures of 1-3 consist of two-dimensional layers of [PbP(S/Se) 4] separated by alkali metal ions. The structure of 1 was solved in the orthorhombic space group Pna2h Compounds 2 and 3 possess the CsSmGeS 4 structure type, crystallizing in the orthorhombic space group R212121. All compounds were refined as racemic twins. All chalcogen sites around the tetrahedrally coordinated P atoms show mixed S/Se occupancy; however, there is a preference for Se binding to Pb ions and S binding to alkali ions. A 31P magic angle spinning NMR study on 1 suggests that, in mixed seleno-/thiophosphates, all of the anions [PS xSe4-x]3- (x= 0,1,2,3,4) are present. The different amount of sulfur and selenium present in KPbPS1.84Se 2.16 (1), RbPbPSL1.56Se2.43 (2), and CsPbPS3.46Se0.54 (3) is reflected in the solid state absorption spectra from which bandgaps of 2.2 eV were determined for 1 and 2, and a blue-shift to 2.5 eV was observed because of the higher sulfurcontent in 3. Thermogravimetric analysis experiments indicated that, upon heating, compound 1 decomposes forming PbSe and sulfur together with other unidentified products. A Raman spectrum of compound 1 showed more bands than are usually observed in seleno- or thiophosphate salts and is another indicator of the mixed seleno-Zthiophosphate anions found in 1.

Original languageEnglish
Pages (from-to)9036-9040
Number of pages5
JournalInorganic Chemistry
Volume48
Issue number18
DOIs
Publication statusPublished - Sep 21 2009

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Selenium
selenium
Sulfur
Anions
Chalcogens
sulfur
Ions
anions
Alkali Metals
solid state
acids
Magic angle spinning
Acids
Alkalies
blue shift
alkali metals
metal spinning
Metal ions
Thermogravimetric analysis
Raman scattering

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Soft-hard acid-base interactions : Probing coordination preferences of sulfur and selenium in mixed chalcophosphates in the family APbPS 4-xSex (A=K, Rb, Cs; x=0-4). / Rothenberger, Alexander; Morris, Collin; Wang, Hsien Hau; Chung, Duck Young; Kanatzidis, Mercouri G.

In: Inorganic Chemistry, Vol. 48, No. 18, 21.09.2009, p. 9036-9040.

Research output: Contribution to journalArticle

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abstract = "The synthesis and structures of the three new compounds, KPbPSL 1.84Se2.16 (1), RbPbPSL1.56Se2.43 (2), and CsPbPS3.46Se0.54 (3), are reported. The solid state structures of 1-3 consist of two-dimensional layers of [PbP(S/Se) 4] separated by alkali metal ions. The structure of 1 was solved in the orthorhombic space group Pna2h Compounds 2 and 3 possess the CsSmGeS 4 structure type, crystallizing in the orthorhombic space group R212121. All compounds were refined as racemic twins. All chalcogen sites around the tetrahedrally coordinated P atoms show mixed S/Se occupancy; however, there is a preference for Se binding to Pb ions and S binding to alkali ions. A 31P magic angle spinning NMR study on 1 suggests that, in mixed seleno-/thiophosphates, all of the anions [PS xSe4-x]3- (x= 0,1,2,3,4) are present. The different amount of sulfur and selenium present in KPbPS1.84Se 2.16 (1), RbPbPSL1.56Se2.43 (2), and CsPbPS3.46Se0.54 (3) is reflected in the solid state absorption spectra from which bandgaps of 2.2 eV were determined for 1 and 2, and a blue-shift to 2.5 eV was observed because of the higher sulfurcontent in 3. Thermogravimetric analysis experiments indicated that, upon heating, compound 1 decomposes forming PbSe and sulfur together with other unidentified products. A Raman spectrum of compound 1 showed more bands than are usually observed in seleno- or thiophosphate salts and is another indicator of the mixed seleno-Zthiophosphate anions found in 1.",
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AB - The synthesis and structures of the three new compounds, KPbPSL 1.84Se2.16 (1), RbPbPSL1.56Se2.43 (2), and CsPbPS3.46Se0.54 (3), are reported. The solid state structures of 1-3 consist of two-dimensional layers of [PbP(S/Se) 4] separated by alkali metal ions. The structure of 1 was solved in the orthorhombic space group Pna2h Compounds 2 and 3 possess the CsSmGeS 4 structure type, crystallizing in the orthorhombic space group R212121. All compounds were refined as racemic twins. All chalcogen sites around the tetrahedrally coordinated P atoms show mixed S/Se occupancy; however, there is a preference for Se binding to Pb ions and S binding to alkali ions. A 31P magic angle spinning NMR study on 1 suggests that, in mixed seleno-/thiophosphates, all of the anions [PS xSe4-x]3- (x= 0,1,2,3,4) are present. The different amount of sulfur and selenium present in KPbPS1.84Se 2.16 (1), RbPbPSL1.56Se2.43 (2), and CsPbPS3.46Se0.54 (3) is reflected in the solid state absorption spectra from which bandgaps of 2.2 eV were determined for 1 and 2, and a blue-shift to 2.5 eV was observed because of the higher sulfurcontent in 3. Thermogravimetric analysis experiments indicated that, upon heating, compound 1 decomposes forming PbSe and sulfur together with other unidentified products. A Raman spectrum of compound 1 showed more bands than are usually observed in seleno- or thiophosphate salts and is another indicator of the mixed seleno-Zthiophosphate anions found in 1.

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