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Assembling Di- and Polynuclear Cu(I) Complexes with Rigid Thioxanthone-Based Ligands: Structures, Reactivity, and
Mohammad Zafar1, Vasudevan Subramaniyan1, Kamal Uddin Ansari1
1Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem 9190401, Israel.
Inorganic Chemistry
|December 16, 2024
Summary
This study reveals a novel thioxanthone-based pincer ligand (L1) that uniquely forms dimeric copper(I) complexes. These complexes exhibit unusual reactivity and phosphorescence, originating from metal-ligand charge transfer in polynuclear copper halide clusters.
Area of Science:
- Coordination Chemistry
- Photophysics
- Organometallic Chemistry
Background:
- Thioxanthone (TX) derivatives are known photoactive compounds, but luminescent systems combining TX with transition metals are scarce.
- A recently developed TX-based PSP pincer ligand (L1) presents an opportunity to explore this area.
- Understanding metal-ligand interactions is crucial for designing new functional materials.
Purpose of the Study:
- To investigate the coordination behavior of the TX-based PSP pincer ligand (L1) with copper(I) ions.
- To characterize the resulting copper complexes and explore their photophysical properties.
- To elucidate the factors governing the ligand's unique assembly and reactivity.
Main Methods:
- Synthesis and characterization of copper(I) complexes with the L1 ligand.
- Crystallographic analysis to determine the structures of the dimeric and polynuclear complexes.
- Photoluminescence spectroscopy and time-dependent density functional theory (TD-DFT) calculations to study emission properties and mechanisms.
Main Results:
- The L1 ligand exclusively forms dimeric copper(I) structures with di- or polynuclear cores.
- Complexes with cationic Cu(I) precursors show facile chloroform C-Cl bond activation, suggesting metal-metal cooperation.
- Dimeric complexes with polynuclear [CuX]n cores (X=Br, I) exhibit phosphorescence attributed to halide-metal-to-ligand charge transfer.
Conclusions:
- The TX-based PSP pincer ligand (L1) displays a unique polynucleating behavior with Cu(I), leading to novel dimeric structures.
- These complexes possess intriguing photoluminescent properties and reactivity, distinct from mononuclear analogues.
- The findings highlight the potential of L1 as a platform for developing new luminescent copper complexes.
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