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A coordination polymer of copper(I) iodide with 6⁵4 topology constructed from Cu₄I₄(DABCO)₄
Summary:
The authors from State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University (P. R. China) developed a zeolite-like copper(I) iodide coordination polymer (Cu₄I₄(DABCO)₂-β) with 6⁵4 topology and self-penetration, achieving results in studying photoluminescent and thermal stability properties.
Background:
1. To address the need for inorganic–organic hybrid materials with novel topologies in coordination chemistry, previous researchers synthesized copper halides with rich photoluminescent properties, yet most tetrahedral four-connected frameworks showed common diamond or diamond-like nets, lacking unique 6⁵4 topology and self-penetration.
2. The authors proposed using Cu₄I₄(DABCO)₄ as a secondary building unit (SBU) with a changed copper source via solvothermal method, obtaining Cu₄I₄(DABCO)₂-β with 6⁵4 topology and self-penetration.
Research Content:
1. Synthesis: The authors synthesized Cu₄I₄(DABCO)₂-β using solvothermal method—mixing Cu(CH₃COO)₂·H₂O, HIO₄·2H₂O, NaClO₄·H₂O, C₆H₁₂N₂·6H₂O in ethanol, stirring 3h, heating at 180℃ for 72h in an autoclave, yielding yellow rhombic blocks (40% yield based on Cu(CH₃COO)₂·H₂O).
2. Characterizations:
1) BET/porosity: Total void volume 43.6%, accessible void volume 4.3%; largest channel diameter 6.8Å (4.4Å with van der Waals radius).
2) SEM/TEM: Not mentioned in the literature.
3) Other tests: Photoluminescence (excitation peak 392nm, emission peak 578nm); thermal analysis (stable up to ~220℃, decomposes 220–455℃ to CuO); X-ray diffraction (orthorhombic Ibam, a=18.473(4)Å, b=37.249(7)Å, c=15.502(3)Å, V=10667(4)ų, Z=16, Dc=2.456g/cm³, R1=0.0771, wR2=0.2100).
3. Application: Not mentioned in the literature.
4. Mechanism: Photoluminescence attributed to triplet “cluster centered” (³CC*) excited state (involves ³XMCT* and ³MCC*); self-penetration due to special shortest circuit configuration in 6⁵4 net.
Outlook:
This research successfully synthesizes a novel 3D zeolite-like copper(I) iodide polymer, enriches zeolite-like material systems, and provides new ideas for functional coordination polymer design.
A coordination polymer of copper(I) iodide with 6⁵4 topology constructed from Cu₄I₄(DABCO)₄
Authors: Minghui Bi, Guanghua Li, Jia Hua, Xiaomin Liu, Yawei Hu, Zhan Shi*, Shouhua Feng
DOI: 10.1039/b709852a
Link: https://pubs.rsc.org/en/content/articlelanding/2007/ce/b709852a
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