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Aggregation Game: Changing Solid-State Emission Using Different Counterions in Monoalkynylphosphonium Pt(II)
Aleksandra Paderina1, Sofia Slavova2, Elena Tupikina1
1Institute of Chemistry, St Petersburg University, Universitetskii pr. 26, St. Petersburg 198504, Russia.
Inorganic Chemistry
|September 6, 2024
Summary
Platinum(II) complexes with terpyridine and phenylbipyridine ligands show tunable triplet luminescence. Anion size significantly impacts solid-state photophysics and platinum-platinum distances in these phosphonium-based materials.
Area of Science:
- Coordination Chemistry
- Photophysics
- Materials Science
Background:
- Heteroleptic platinum(II) complexes are investigated for their luminescent properties.
- Tuning ligand environments in platinum(II) complexes can modulate photophysical behavior.
Purpose of the Study:
- To synthesize and characterize two series of heteroleptic monoalkynylphosphonium Pt(II) complexes.
- To investigate the influence of ligand structure and counteranions on photophysical properties in solution and solid state.
Main Methods:
- Spectroscopic characterization (e.g., UV-Vis absorption, emission spectroscopy).
- Density Functional Theory (DFT) calculations for electronic structure analysis.
- Investigation of solid-state luminescence and anion effects.
Main Results:
- Complexes exhibit triplet emission in solution and solid state, dependent on ligand and composition.
- DFT analysis reveals MLCT, ILCT, and LLCT transitions.
- Solid-state luminescence involves LC, MLCT, MMLCT, and MC transitions, influenced by Pt⋯Pt interactions.
- Anion variation significantly alters photophysical properties of terpyridine-based complexes, showing a dependence on anion size.
Conclusions:
- The photophysical properties of these Pt(II) complexes are tunable through ligand design and counteranion selection.
- Anion size plays a crucial role in modulating solid-state luminescence and Pt⋯Pt distances.
- Quantum chemical modeling provides insights into anion-controlled solid-state packing and electronic properties.
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