Powerful templating effect in Rb/Pd/Se(x) promoted by crown ether-like [Rb(Se8)]+ coordination. Formation of Rb2[Pd(Se4)2] · Se8: A layered Pd polyselenide with 'encapsulated' eight-membered selenium rings

Michael Wachhold, Mercouri G Kanatzidis

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20 Citations (Scopus)

Abstract

A novel layered Rb-Pd polyselenide has been synthesized by methanothermal reaction of Pd2+ with Se(x)2- (from Se2- + Se) in the presence of Rb2CO3. Rb2[Pd(Se4)2] · Se8 (I) reveals a unique structure with infinite [Pd(Se4)2]2- sheet polyanions acting as a host for neutral Se8 rings. The black shiny rectangular crystals of Rb2[Pd(Se4)2] · Se8 are insoluble in H2O and common organic solvents. The compound crystallizes in the noncentrosymmetric space group P4b2 (No. 117) with a = 12.6748(8) Å, c = 6.9273(7) Å, Z = 2, and V = 1112.9(2) Å3. The [Pd(Se4)2]2- sheet anion contains Pd2+ ions with a distorted square planar coordination geometry to four terminal Se atoms of Se4 2- chains. The cocrystallized neutral Se8 rings have a crown-like conformation as known from the elemental Se8 forms. Through coordination to Rb+ ions they build [Rb(Se8)+](n) 'cationic chains' running in the c direction. Rb2[Pd(Se4)2] · Se8 therefore differs fundamentally from its 'neighboring' alkali metal Pd polyselenides, K2PdSe10 and Cs2PdSe8, which each possess a three- dimensional structure with two interpenetrating [Pd(Se(x))2]2- frameworks. Optical spectroscopic data and the thermal stability of the compound are discussed.

Original languageEnglish
Pages (from-to)4189-4195
Number of pages7
JournalJournal of the American Chemical Society
Volume121
Issue number17
DOIs
Publication statusPublished - May 5 1999

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Crown Ethers
Crown ethers
Selenium
Ions
Alkali Metals
Alkali metals
Crowns
Organic solvents
Anions
Conformations
Thermodynamic stability
Negative ions
Hot Temperature
Atoms
Crystals
Geometry
polyanions
Direction compound

ASJC Scopus subject areas

  • Chemistry(all)

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title = "Powerful templating effect in Rb/Pd/Se(x) promoted by crown ether-like [Rb(Se8)]+ coordination. Formation of Rb2[Pd(Se4)2] · Se8: A layered Pd polyselenide with 'encapsulated' eight-membered selenium rings",
abstract = "A novel layered Rb-Pd polyselenide has been synthesized by methanothermal reaction of Pd2+ with Se(x)2- (from Se2- + Se) in the presence of Rb2CO3. Rb2[Pd(Se4)2] · Se8 (I) reveals a unique structure with infinite [Pd(Se4)2]2- sheet polyanions acting as a host for neutral Se8 rings. The black shiny rectangular crystals of Rb2[Pd(Se4)2] · Se8 are insoluble in H2O and common organic solvents. The compound crystallizes in the noncentrosymmetric space group P4b2 (No. 117) with a = 12.6748(8) {\AA}, c = 6.9273(7) {\AA}, Z = 2, and V = 1112.9(2) {\AA}3. The [Pd(Se4)2]2- sheet anion contains Pd2+ ions with a distorted square planar coordination geometry to four terminal Se atoms of Se4 2- chains. The cocrystallized neutral Se8 rings have a crown-like conformation as known from the elemental Se8 forms. Through coordination to Rb+ ions they build [Rb(Se8)+](n) 'cationic chains' running in the c direction. Rb2[Pd(Se4)2] · Se8 therefore differs fundamentally from its 'neighboring' alkali metal Pd polyselenides, K2PdSe10 and Cs2PdSe8, which each possess a three- dimensional structure with two interpenetrating [Pd(Se(x))2]2- frameworks. Optical spectroscopic data and the thermal stability of the compound are discussed.",
author = "Michael Wachhold and Kanatzidis, {Mercouri G}",
year = "1999",
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T2 - A layered Pd polyselenide with 'encapsulated' eight-membered selenium rings

AU - Wachhold, Michael

AU - Kanatzidis, Mercouri G

PY - 1999/5/5

Y1 - 1999/5/5

N2 - A novel layered Rb-Pd polyselenide has been synthesized by methanothermal reaction of Pd2+ with Se(x)2- (from Se2- + Se) in the presence of Rb2CO3. Rb2[Pd(Se4)2] · Se8 (I) reveals a unique structure with infinite [Pd(Se4)2]2- sheet polyanions acting as a host for neutral Se8 rings. The black shiny rectangular crystals of Rb2[Pd(Se4)2] · Se8 are insoluble in H2O and common organic solvents. The compound crystallizes in the noncentrosymmetric space group P4b2 (No. 117) with a = 12.6748(8) Å, c = 6.9273(7) Å, Z = 2, and V = 1112.9(2) Å3. The [Pd(Se4)2]2- sheet anion contains Pd2+ ions with a distorted square planar coordination geometry to four terminal Se atoms of Se4 2- chains. The cocrystallized neutral Se8 rings have a crown-like conformation as known from the elemental Se8 forms. Through coordination to Rb+ ions they build [Rb(Se8)+](n) 'cationic chains' running in the c direction. Rb2[Pd(Se4)2] · Se8 therefore differs fundamentally from its 'neighboring' alkali metal Pd polyselenides, K2PdSe10 and Cs2PdSe8, which each possess a three- dimensional structure with two interpenetrating [Pd(Se(x))2]2- frameworks. Optical spectroscopic data and the thermal stability of the compound are discussed.

AB - A novel layered Rb-Pd polyselenide has been synthesized by methanothermal reaction of Pd2+ with Se(x)2- (from Se2- + Se) in the presence of Rb2CO3. Rb2[Pd(Se4)2] · Se8 (I) reveals a unique structure with infinite [Pd(Se4)2]2- sheet polyanions acting as a host for neutral Se8 rings. The black shiny rectangular crystals of Rb2[Pd(Se4)2] · Se8 are insoluble in H2O and common organic solvents. The compound crystallizes in the noncentrosymmetric space group P4b2 (No. 117) with a = 12.6748(8) Å, c = 6.9273(7) Å, Z = 2, and V = 1112.9(2) Å3. The [Pd(Se4)2]2- sheet anion contains Pd2+ ions with a distorted square planar coordination geometry to four terminal Se atoms of Se4 2- chains. The cocrystallized neutral Se8 rings have a crown-like conformation as known from the elemental Se8 forms. Through coordination to Rb+ ions they build [Rb(Se8)+](n) 'cationic chains' running in the c direction. Rb2[Pd(Se4)2] · Se8 therefore differs fundamentally from its 'neighboring' alkali metal Pd polyselenides, K2PdSe10 and Cs2PdSe8, which each possess a three- dimensional structure with two interpenetrating [Pd(Se(x))2]2- frameworks. Optical spectroscopic data and the thermal stability of the compound are discussed.

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