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.
| Original language | English |
|---|---|
| Pages (from-to) | 4934-4941 |
| Number of pages | 8 |
| Journal | Inorganic Chemistry |
| Volume | 49 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - 2010 Jun 7 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
Cite this
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 journal › Article
}
TY - JOUR
T1 - Structure, Photophysical Properties, and DFT Calculations of Selenide-Centered Pentacapped Trigonal Prismatic Silver(I) Clusters
AU - Liu, C. W.
AU - Feng, Ching Shiang
AU - Fu, Rei Jen
AU - Chang, Hao Wei
AU - Saillard, Jean Yves
AU - Kahlal, Samia
AU - Wang, Ju Chun
AU - Chang, I-Jy
PY - 2010/6/7
Y1 - 2010/6/7
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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U2 - 10.1021/ic902571q
DO - 10.1021/ic902571q
M3 - Article
VL - 49
SP - 4934
EP - 4941
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 11
ER -