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[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
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Copper(I) Alkynyl Clusters with Crystallization-Induced Emission Enhancement
Jun-Jie Fang1, Yang-Lin Shen1, Zheng Liu1
1State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.
Inorganic Chemistry
|August 19, 2021
Summary
New copper(I) alkynyl complexes with phosphate ligands show strong luminescence in their crystalline state. This crystallization-induced emission enhancement is linked to ligand interactions and offers potential for photocurrent applications.
Area of Science:
- Coordination Chemistry
- Materials Science
- Supramolecular Chemistry
Background:
- Copper(I) alkynyl complexes are of interest due to their diverse structures and potential applications.
- Phosphate ligands can influence the assembly and properties of metal complexes.
- Crystallization-induced emission enhancement is a phenomenon observed in some solid-state materials.
Purpose of the Study:
- To synthesize and characterize novel copper(I) alkynyl complexes incorporating phosphate ligands.
- To investigate the structural features and luminescence properties of these complexes.
- To explore the relationship between crystal structure and emission enhancement.
Main Methods:
- Solvothermal synthesis of four copper(I) alkynyl complexes.
- Characterization using IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction.
- Analysis of luminescence properties in crystalline, amorphous, and solution states.
Main Results:
- Synthesis of [Cu16(tBuC≡C)12(PhOPO3)2] (1), [Cu16(tBuC≡C)12(1-NaphOPO3)2] (2), [VO4@Cu25(tBuC≡C)19(1-NaphOPO3)](PF6)0.5(F)0.5 (3), and [PO4@Cu25(tBuC≡C)19(1-NaphOPO3)](PF6)0.5(F)0.5 (4).
- Complexes 1 and 2 form coordination chain polymers, while 3 and 4 feature high-nuclearity copper(I) clusters encapsulating template ions.
- All complexes exhibit significant crystallization-induced emission enhancement, with strong luminescence in the crystalline state compared to amorphous or solution states.
- C-H···π and π···π interactions are identified as key factors for enhanced emission.
- Clusters 3 and 4 demonstrate photocurrent responses under visible-light illumination.
Conclusions:
- The study successfully synthesized and characterized novel copper(I) alkynyl complexes with phosphate ligands.
- Crystallization-induced emission enhancement is a prominent feature, attributed to specific intermolecular interactions.
- The high-nuclearity copper(I) clusters show potential for optoelectronic applications, evidenced by their photocurrent response.
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