title: Structure, photophysical properties, and DFT calculations of selenide-centered pentacapped trigonal prismatic silver(I) clusters.
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.
authors.affiliation: Department of Chemistry, National Dong Hwa University, Hualien, Taiwan 97401, Republic of China. chenwei@mail.ndhu.edu.tw
authors.forename: C W
authors.initials: CW
authors.lastname: Liu
authors.forename: Ching-Shiang
authors.initials: CS
authors.lastname: Feng
authors.forename: Rei-Jen
authors.initials: RJ
authors.lastname: Fu
authors.forename: Hao-Wei
authors.initials: HW
authors.lastname: Chang
authors.forename: Jean-Yves
authors.initials: JY
authors.lastname: Saillard
authors.forename: Samia
authors.initials: S
authors.lastname: Kahlal
authors.forename: Ju-Chun
authors.initials: JC
authors.lastname: Wang
authors.forename: I-Jy
authors.initials: IJ
authors.lastname: Chang
mesh_terms: D003198:Computer Simulation; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010777:Photochemistry; D012643:Selenium / Q000737:chemistry*; D012834:Silver / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D009942:Organometallic Compounds; D012834:Silver; D012643:Selenium