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Heterocluster-Assembled Crystalline Hydrophobic Complexes with Delayed Fluorescence.
Jing He1,2,3, Liang He1, Minyi Zhang1
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
Advanced Materials (Deerfield Beach, Fla.)
|June 4, 2025
Summary
Researchers developed a new method to create stable metal-organic frameworks (MOFs) with metal-sulfur bonds. This approach enables the synthesis of complex heterocluster MOFs with tunable optoelectronic properties for advanced materials.
Area of Science:
- Materials Science
- Chemistry
- Nanotechnology
Background:
- Metal-organic frameworks (MOFs) with metal-sulfur bonds offer unique electrical, redox, and optical properties.
- Rapid nucleation during crystallization has limited the development of these MOFs.
- Controlling MOF synthesis is crucial for achieving desired network topologies and functionalities.
Purpose of the Study:
- To overcome the challenge of rapid nucleation in metal-sulfur MOF synthesis.
- To develop a modulator-assisted strategy for constructing diverse MOF structures, including heteroclusters.
- To design novel MOFs with tailored optoelectronic properties, such as thermally activated delayed fluorescence (TADF).
Main Methods:
- Utilized amine-based modulators to retard nucleation during MOF crystallization.
- Synthesized a series of Cu-S cluster-based MOFs using diverse network topologies.
- Fabricated [Sn4]-based MOFs using donor-acceptor ligands and explored disulfide linkage formation.
Main Results:
- Successfully synthesized six Cu-S cluster-based MOFs with varied network topologies.
- Developed two [Sn4]-based MOFs, revealing novel dicarboxylate ligands with disulfide linkages.
- Pioneered the first bimetallic heterocluster MOF (SnCu-mMBA-dia) with both metal-oxygen and metal-sulfur clusters, exhibiting TADF and exceptional hydrolytic stability.
Conclusions:
- The modulator-assisted strategy effectively controls nucleation, enabling the synthesis of complex MOFs.
- The novel heterocluster MOF demonstrates promising properties for luminescent materials.
- This work provides a new paradigm for designing stable, functional MOFs with tailored optoelectronic applications.
