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Double-Decker Platinum Complexes: From Visible to NIR-II Luminescence
Irene Melendo1, Pilar Borja1, Sara Fuertes1
1Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC - Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain.
Inorganic Chemistry
|August 22, 2025
Summary
This study synthesized platinum(II) and platinum(III) dinuclear compounds. The platinum(III) complexes exhibit shorter platinum-platinum bonds and emit light in the NIR-II region, unlike platinum(II) compounds.
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.
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