Abstract
The title compounds were obtained from the reactions of copper or silver monohalides with the bidentate bis(diphenylphosphino)methane (dppm) ligand at room temperature in a mixed solvent. Single-crystal X-ray diffraction analyses indicate that both compounds crystallize in a monoclinic system but in different space groups. The structures are characterized by a trinuclear [M 3I2(dppm)3] + cation with a trigonal-bipyramid [M3(μ3-I)2] core. In agreement with the geometric characteristics of the M3 triangles, 31P NMR spectra exhibit a single peak for the [Cu3] cluster but a double peak for the [Ag3] cluster. Preliminary optical studies by UV/Vis and emission techniques show major absorption shoulders at ∼ 286 nm for Cu3I2(dppm)3·I and ∼ 254 nm for Ag3I2(dppm)3·I, but no luminescence in the non-degassed MeCN solution at 298 K. The structures, bonding, electronic excitations and emissions are discussed based on relativistic density functional theory calculations.
Original language | English (US) |
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Pages (from-to) | 119-136 |
Number of pages | 18 |
Journal | Journal of Cluster Science |
Volume | 13 |
Issue number | 1 |
DOIs | |
State | Published - Dec 1 2002 |
Keywords
- Ag
- Cu
- Electronic structures
- Halides
- Optical properties
- Trinuclear clusters
- dppm