The incorporation of heterovalent copper-oxo and copper-halide clusters for the fabrication of three porous cluster organic frameworks: syntheses, structures and iodine adsorption/release study

• Published in: CrystEngComm 2020, Vol.22 (4), p.821-828
• Main Authors: Liu, Jin-Hua, Zhang, Jing, Zhao, Dan, Lin, Li-Dan, Sun, Yan-Qiong, Li, Xin-Xiong, Zheng, Shou-Tian
• Format: Article
• Language: English
• Subjects: Adsorption; Benzoic acid; Carbon dioxide; Clusters; Construction planning; Copper; Crystal structure; Crystallography; Crystals; Iodine; Organic chemistry
• ISSN: 1466-8033; 1466-8033
• DOI: 10.1039/c9ce01745c

Three porous heterovalent cluster organic frameworks Cu 2 (H 2 O)(Cu 4 I 4 )(INA) 4 ·solvent ( 1 ), Cu 2 (H 2 O) 2 (Cu 4 I 4 ) 2 (INA) 4 (DABCO) 2 ·2DMA ( 2 ) and [(Cu 2 ) 2 (PVBA) 8 (Cu 4 I 4 )]·DMF ( 3 ) (HINA = isonicotinic acid, DABCO = 1,4-diazabicyclo[2.2.2]octane, HPVBA = 4-(2-(4-pyridyl)ethenyl) benzoic acid, DMF = N , N ′-dimethylformamide, DMA = N , N ′-dimethylacetamide) have been solvothermally synthesized and structurally characterized. Crystal structure analyses indicate that compounds 1 and 2 are constructed from planar four-connected Cu 2 (CO 2 ) 4 secondary building units (SBUs) and tetrahedral four-connected Cu 4 I 4 SBUs, while compound 3 is composed of octahedral six-connected Cu 2 (CO 2 ) 4 SBUs and tetrahedral four-connected Cu 4 I 4 SBUs. All these frameworks possess nano-sized 1-dimensional channels. Furthermore, the thermal and chemical stabilities, gas adsorption properties and iodine adsorption/release ability of compound 2 have been systematically studied. Three porous cluster organic frameworks constructed from the paddle-wheel Cu 2 (CO 2 ) 4 and cubane-like Cu 4 I 4 clusters have been synthesized and characterized. Interestingly, compound 2 shows moderate gas uptake ability and I 2 adsorption/release feature.