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Luminescent MTN-Type Cluster−Organic Framework with 2.6 nm Cages
Summary:
The authors from State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences (China) and Department of Chemistry and Biochemistry, California State University, Long Beach (USA) developed the MTN-type cluster-organic framework COZ-1 with giant cages and luminescent properties, achieving integration of porosity and photoluminescence in porous materials.
Background:
1. To address the issues of small pore size and limited tetrahedrally coordinated atoms in traditional zeolite frameworks, and the rarity of zeolite-type structures based on halide clusters, previous researchers explored zeolitic MOFs but faced challenges in synthesizing iodide cluster-based zeolite-type frameworks.
2. The authors proposed using tetrahedral Cu₄I₄ clusters as pseudotetrahedral units with dabco ligands, successfully constructing COZ-1 with MTN topology and dual properties of porosity and luminescence.
Research Content:
1.Synthesis: The authors synthesized COZ-1 via solvothermal method—mixing CuI, dabco, hypoxanthine in DMF/ethanol, adding triethylamine, heating at 100 °C for 15 days.
2.Characterizations:
1) BET: Langmuir surface area 728 m²/g, BET 514 m²/g; pore size: median 1.53 nm, BJH adsorption average 2.52 nm.
2) No SEM/TEM tests mentioned.
3) Optical test: Emission max at 588 nm under 350 nm UV excitation; TGA: Guest molecules removed below 150 °C.
3.Application: No specific application tests mentioned.
4.Mechanism: Emission from "cluster-centered" triplet excited state (iodide-to-metal charge transfer + d¹⁰Cu→d⁹s¹Cu character); Cu₄I₄ clusters and dabco form MTN framework with porosity.
Outlook:
This research successfully synthesized COZ-1 with giant cages, realizing integration of porosity and luminescence, providing a new path for designing functional cluster-organic frameworks.
Luminescent MTN-Type Cluster−Organic Framework with 2.6 nm Cages
Authors: Yao Kang, Fei Wang, Jian Zhang, Xianhui Bu
DOI: 10.1021/ja308801n
Link: https://pubs.acs.org/doi/10.1021/ja308801n
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