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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Photophysics

Background:

  • Dinuclear platinum complexes are of interest for their unique structural and photophysical properties.
  • Understanding the relationship between structure, oxidation state, and luminescence is crucial for developing new materials.

Purpose of the Study:

  • To synthesize and characterize novel dinuclear platinum(II) and platinum(III) compounds.
  • To investigate the structural differences, particularly the platinum-platinum bond, between the two oxidation states.
  • To explore the photophysical properties, including emission wavelengths and electronic transitions, of these complexes.

Main Methods:

  • Synthesis of mononuclear platinum precursors followed by dimerization to form Pt(II) dinuclear complexes.
  • Oxidation of Pt(II) complexes to Pt(III) dinuclear derivatives using aqueous hydrohalic acids.
  • X-ray crystallography for structural determination.
  • Experimental and theoretical (DFT, TD-DFT) studies of photophysical properties.

Main Results:

  • Successfully synthesized Pt(II) dinuclear complexes [{Pt(C^N)(μ-S^N)}₂] and their oxidized Pt(III) counterparts [{Pt(C^N)(μ-S^N)X}₂].
  • X-ray structures reveal shorter Pt-Pt distances (ca. 2.7 Å) in Pt(III) complexes compared to Pt(II) complexes (ca. 3.0 Å), indicating a Pt-Pt bond in the former.
  • Pt(II) complexes emit in the visible region (640-685 nm) with 3ππ* and 3MMLCT character.
  • Pt(III) complexes exhibit emission in the NIR-II region (up to 1215 nm) with 3XMMCT character, influenced by axial ligands and orbital overlap.

Conclusions:

  • The oxidation state significantly impacts the Pt-Pt bond length and photophysical properties of dinuclear platinum complexes.
  • Pt(III) complexes with Pt-Pt bonds show distinct NIR-II emission attributed to 3XMMCT transitions.
  • The emission energies are tunable by axial ligands and the nature of the ancillary ligands, offering potential for optoelectronic applications.