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 journalArticlepeer-review

24 Citations (Scopus)

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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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