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

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

Inorg Chem. 2010 Jun 7;49(11):4934-41.

PMID: 20459139

Abstract:

Undecanuclear silver clusters [Ag(11)(mu(9)-Se)(mu(3)-Br)(3){Se(2)P(OR)(2)}(6)] (R = Et, (i)Pr, (2)Bu) were isolated from the reaction of [Ag(CH(3)CN)(4)](PF(6)), NH(4)[Se(2)P(OR)(2)], and Bu(4)NBr in a molar ratio of 4:3:1 in CH(2)Cl(2) at -20 degrees C. Clusters were characterized by elemental analysis, NMR spectroscopy ((1)H, (31)P, and (77)Se), positive FAB mass spectrometry, and X-ray crystallography of the isopropyl derivative. Structural elucidations revealed that the Ag(11)Se 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 (mu(2), mu(2)) coordination mode, and three mu(3)-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 [Ag(11)(mu(9)-Se)(mu(3)-Br)(3){Se(2)P(O(i)Pr)(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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP1302096	Silver(I) selenide		1302-09-6	Price

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