Structure, Photophysical Properties, and DFT Calculations of Selenide-Centered Pentacapped Trigonal Prismatic Silver(I) Clusters

C. W. Liu, Ching Shiang Feng, Rei Jen Fu, Hao Wei Chang, Jean Yves Saillard, Samia Kahlal, Ju Chun Wang, I-Jy Chang

Research output: Contribution to journalArticle

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Abstract

Undecanuclear silver clusters [Ag119-Se) (μ3-Br)3{Se2P(OR)2}6] (R = Et, iPr, 2Bu) were isolated from the reaction of [Ag(CH3CN)4](PF6), NH4[Se 2P(OR)2], and Bu4NBr in a molar ratio of 4:3:1 in CH2Cl2 at-20 ̊C. Clusters were characterized by elemental analysis, NMR spectroscopy (1H, 31P, and 77Se), positive FAB mass spectrometry, and X-ray crystallography of the isopropyl derivative. Structural elucidations revealed that the Ag 11Se core geometry of clusters is a selenide-centered, slightly distorted 3,3,4,4,4-pentacapped trigonal prism surrounded by six diselenophosphato ligands, each in a tetrametallic tetraconnective (μ2, μ2) coordination mode, and three μ3-bromide anions. All compounds exhibited orange luminescence both as a solid and in solution. The electronic structure of these clusters was studied by DFT calculations, and their optical properties were rationalized through a TDDFT investigation. The computed metrical parameters of the clusters were consistent with the corresponding X-ray data of [Ag119-Se)(μ3-Br)3{Se2P(O iPr)2}6]. The theoretical investigations affirmed that the low-energy absorptions as well as emissions were due to transitions from an orbital mostly of a selenophosphate ligand/central Se atom character to an orbital of metal character.

Original languageEnglish
Pages (from-to)4934-4941
Number of pages8
JournalInorganic Chemistry
Volume49
Issue number11
DOIs
Publication statusPublished - 2010 Jun 7

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selenides
Silver
Discrete Fourier transforms
silver
Ligands
X ray crystallography
X Ray Crystallography
Energy absorption
Prisms
Luminescence
Bromides
Nuclear magnetic resonance spectroscopy
Electronic structure
Anions
Mass spectrometry
Mass Spectrometry
Magnetic Resonance Spectroscopy
Optical properties
Metals
X-Rays

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Structure, Photophysical Properties, and DFT Calculations of Selenide-Centered Pentacapped Trigonal Prismatic Silver(I) Clusters. / Liu, C. W.; Feng, Ching Shiang; Fu, Rei Jen; Chang, Hao Wei; Saillard, Jean Yves; Kahlal, Samia; Wang, Ju Chun; Chang, I-Jy.

In: Inorganic Chemistry, Vol. 49, No. 11, 07.06.2010, p. 4934-4941.

Research output: Contribution to journalArticle

Liu, C. W. ; Feng, Ching Shiang ; Fu, Rei Jen ; Chang, Hao Wei ; Saillard, Jean Yves ; Kahlal, Samia ; Wang, Ju Chun ; Chang, I-Jy. / Structure, Photophysical Properties, and DFT Calculations of Selenide-Centered Pentacapped Trigonal Prismatic Silver(I) Clusters. In: Inorganic Chemistry. 2010 ; Vol. 49, No. 11. pp. 4934-4941.
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abstract = "Undecanuclear silver clusters [Ag11(μ9-Se) (μ3-Br)3{Se2P(OR)2}6] (R = Et, iPr, 2Bu) were isolated from the reaction of [Ag(CH3CN)4](PF6), NH4[Se 2P(OR)2], and Bu4NBr in a molar ratio of 4:3:1 in CH2Cl2 at-20 ̊C. Clusters were characterized by elemental analysis, NMR spectroscopy (1H, 31P, and 77Se), positive FAB mass spectrometry, and X-ray crystallography of the isopropyl derivative. Structural elucidations revealed that the Ag 11Se core geometry of clusters is a selenide-centered, slightly distorted 3,3,4,4,4-pentacapped trigonal prism surrounded by six diselenophosphato ligands, each in a tetrametallic tetraconnective (μ2, μ2) coordination mode, and three μ3-bromide anions. All compounds exhibited orange luminescence both as a solid and in solution. The electronic structure of these clusters was studied by DFT calculations, and their optical properties were rationalized through a TDDFT investigation. The computed metrical parameters of the clusters were consistent with the corresponding X-ray data of [Ag11(μ 9-Se)(μ3-Br)3{Se2P(O iPr)2}6]. The theoretical investigations affirmed that the low-energy absorptions as well as emissions were due to transitions from an orbital mostly of a selenophosphate ligand/central Se atom character to an orbital of metal character.",
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AU - Feng, Ching Shiang

AU - Fu, Rei Jen

AU - Chang, Hao Wei

AU - Saillard, Jean Yves

AU - Kahlal, Samia

AU - Wang, Ju Chun

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N2 - Undecanuclear silver clusters [Ag11(μ9-Se) (μ3-Br)3{Se2P(OR)2}6] (R = Et, iPr, 2Bu) were isolated from the reaction of [Ag(CH3CN)4](PF6), NH4[Se 2P(OR)2], and Bu4NBr in a molar ratio of 4:3:1 in CH2Cl2 at-20 ̊C. Clusters were characterized by elemental analysis, NMR spectroscopy (1H, 31P, and 77Se), positive FAB mass spectrometry, and X-ray crystallography of the isopropyl derivative. Structural elucidations revealed that the Ag 11Se core geometry of clusters is a selenide-centered, slightly distorted 3,3,4,4,4-pentacapped trigonal prism surrounded by six diselenophosphato ligands, each in a tetrametallic tetraconnective (μ2, μ2) coordination mode, and three μ3-bromide anions. All compounds exhibited orange luminescence both as a solid and in solution. The electronic structure of these clusters was studied by DFT calculations, and their optical properties were rationalized through a TDDFT investigation. The computed metrical parameters of the clusters were consistent with the corresponding X-ray data of [Ag11(μ 9-Se)(μ3-Br)3{Se2P(O iPr)2}6]. The theoretical investigations affirmed that the low-energy absorptions as well as emissions were due to transitions from an orbital mostly of a selenophosphate ligand/central Se atom character to an orbital of metal character.

AB - Undecanuclear silver clusters [Ag11(μ9-Se) (μ3-Br)3{Se2P(OR)2}6] (R = Et, iPr, 2Bu) were isolated from the reaction of [Ag(CH3CN)4](PF6), NH4[Se 2P(OR)2], and Bu4NBr in a molar ratio of 4:3:1 in CH2Cl2 at-20 ̊C. Clusters were characterized by elemental analysis, NMR spectroscopy (1H, 31P, and 77Se), positive FAB mass spectrometry, and X-ray crystallography of the isopropyl derivative. Structural elucidations revealed that the Ag 11Se core geometry of clusters is a selenide-centered, slightly distorted 3,3,4,4,4-pentacapped trigonal prism surrounded by six diselenophosphato ligands, each in a tetrametallic tetraconnective (μ2, μ2) coordination mode, and three μ3-bromide anions. All compounds exhibited orange luminescence both as a solid and in solution. The electronic structure of these clusters was studied by DFT calculations, and their optical properties were rationalized through a TDDFT investigation. The computed metrical parameters of the clusters were consistent with the corresponding X-ray data of [Ag11(μ 9-Se)(μ3-Br)3{Se2P(O iPr)2}6]. The theoretical investigations affirmed that the low-energy absorptions as well as emissions were due to transitions from an orbital mostly of a selenophosphate ligand/central Se atom character to an orbital of metal character.

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