Syntheses, structures, bonding, and optical properties of trinuclear cluster iodides: M33-I)2(μ-dppm) 3·I (M = Cu, Ag), dppm = bis(diphenylphosphino)methane)

Wen Bo Zhou, Zhen Chao Dong, Jun Ling Song, Hui Yi Zeng, Rong Cao, Guo Cong Guo, Jin Shun Huang, Jun Li

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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 [M33-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 languageEnglish (US)
Pages (from-to)119-136
Number of pages18
JournalJournal of Cluster Science
Issue number1
StatePublished - Dec 1 2002


  • Ag
  • Cu
  • Electronic structures
  • Halides
  • Optical properties
  • Trinuclear clusters
  • dppm


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