Synthesis, structure, and emission spectroscopy of luminescent Pt(COD)(dithiolate) complexes
- Univ. of Rochester, NY (United States)
The synthesis, characterization, X-ray structure determination and emission spectroscopy of two Pt(COD)(S-S) complexes are reported where COD = 1,5-cycloctadiene (COD) and S-S is maleonitriledithiolate (mnt) for complex 1 and 1-(ethoxycarbonyl)-1-cyanoethylene-2,2-dithiolate (ecda) for complex 2. Both complexes are isolated in high yield from the reaction of Pt(COD)Cl{sub 2} and the corresponding dianionic dithiolate salt. Orange crystals of 1 (C{sub 12}H{sub 12}N{sub 2}PtS{sub 2}) are monoclinic, space group P2{sub 1}/n (No. 14). Each complex possess a square planar structure with chelating diolefin and dithiolate ligands. Proton NMR spectroscopy shows that the solid-state structures are maintained in solution. The complexes are luminescent at low temperature in the solid state and in frozen glasses. In the solid state at 77 K, Pt(COD)(mnt) exhibits a highly structured emission ({lambda}{sub max} = 560 nm, 17.9 kcm{sup {minus}1}) with a vibronic progression of {approximately}1400 cm{sup {minus}1}, whereas for Pt(COD)(ecda), the emission is broad and featureless ({lambda}{sub max} = 525 nm, 19.0 kcm{sup {minus}1}). The emissive state for both complexes is assigned as a metal-to-dithiolate charge transfer with differences in the structure and energy of the emissions resulting from differences in the {pi}*{sub dithiolate} orbital of the mnt and ecda ligands.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 75698
- Journal Information:
- Inorganic Chemistry, Vol. 32, Issue 17; Other Information: PBD: 18 Aug 1993
- Country of Publication:
- United States
- Language:
- English
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