Palladium(II) and platinum(II) analogues of luminescent diimine triangulo complexes supported by triply bridging sulfide ligands : Structural and spectroscopic comparisons

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

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Author(s)

  • B. C. Tzeng
  • S. C. Chan
  • C. M. Che
  • K. K. Cheung
  • S. M. Peng

Detail(s)

Original languageEnglish
Pages (from-to)6699-6704
Journal / PublicationInorganic Chemistry
Volume40
Issue number26
Publication statusPublished - 17 Dec 2001
Externally publishedYes

Abstract

Reaction of [M(L-L)Cl2] [M = Pd, Pt; L-L = 4,4′-di-tert-butyl-2,2′-bipyridine (tBu2bpy), 4,4′-dimethylcarboxylate-2,2′-bipyridine ((CO2Me)2bpy), bis(diphenylphosphino)methane (dppm)] with Na2S in refluxing methanol afforded [M3(tBu2bpy)3 (μ3-S)2]2+ [M = Pd (1a), Pt (2a)], [M3((CO2Me)2bpy)33-S)2]2+ [M = Pd (1b), Pt (2b)], and [Pt3(dppm)33-S)2]2+ (3) as perchlorate salts. X-ray crystal analysis revealed that 1a, 1b, 2a, and 3 have triangular M3S2 core structures. The three metal atoms in 1a, 2a, and 3 form virtual equilateral triangles with intramolecular Pd-Pd and Pt-Pt separations of 3.027(1)-3.065(1) and 3.104(1)-3.154(1) Å, respectively. An isosceles triangle of Pd3 atoms is observed in the molecular structure of 1b. The 1MLCT absorption of 2a and 2b appears at 415 and 448 nm, respectively, in dichloromethane and is significantly red-shifted from the lowest energy absorption band of the Pd3 analogues. Complex 1a exhibits weak photoluminescence in the solid state at 77 and 298 K (uncorrected λmax 760 and 730 nm, respectively) while the 77 K solid-state emission of 1b (uncorrected λmax 760 nm) is also weak. At 77 K, complexes 2a, 2b, and 3 display broad unstructured emissions at λmax 616-630 nm in the solid state. Ligand-field excited states are tentatively assigned for these emissions.

Citation Format(s)

Palladium(II) and platinum(II) analogues of luminescent diimine triangulo complexes supported by triply bridging sulfide ligands: Structural and spectroscopic comparisons. / Tzeng, B. C.; Chan, S. C.; Chan, M. C W et al.
In: Inorganic Chemistry, Vol. 40, No. 26, 17.12.2001, p. 6699-6704.

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review