NDLI: Mixed-Ligand Metal–Organic Frameworks with Large Pores: Gas Sorption Properties and Single-Crystal-to-Single-Crystal Transformation on Guest Exchange

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Mixed-Ligand Metal–Organic Frameworks with Large Pores: Gas Sorption Properties and Single-Crystal-to-Single-Crystal Transformation on Guest Exchange

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Mixed-Ligand Metal–Organic Frameworks with Large Pores: Gas Sorption Properties and Single-Crystal-to-Single-Crystal Transformation on Guest Exchange

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Suh, Myunghyun Paik Park, Hye Jeong
Description	Author Affiliation: Park HJ ( Department of Chemistry, Seoul National University, Seoul 151-747, Republic of Korea.)
Abstract	Two isomorphous 3D metal–organic frameworks, $\{[Cu_{2}(BPnDC)_{2}(bpy)]⋅8 DMF⋅6 H_{2}O\}_{n}$ (1) and $\{[Zn_{2}(BPnDC)_{2}(dabco)]⋅13 DMF⋅3 H_{2}O\}_{n}$ (2), have been prepared by the solvothermal reactions of benzophenone 4,4′-dicarboxylic acid $(H_{2}BPnDC)$ with $Cu(NO_{3})_{2}⋅2.5 H_{2}O$ and 4,4′-bipyridine (bpy), and with $Zn(NO_{3})_{2}⋅6 H_{2}O$ and 4-diazabicyclo[2.2.2]octane (dabco), respectively. Compounds 1 and 2 are composed of paddle-wheel $\{M_{2}(O_{2}CR)_{4}\}$ cluster units, and they generate 2D channels with two different large pores (effective size of larger pore: 18.2 Å for 1, 11.4 Å for 2). The framework structure of desolvated solid, $[Cu_{2}(BPnDC)_{2}(bpy)]_{n}$ (SNU-6; SNU=Seoul National University), is the same as that of 1, as evidenced by powder X-ray diffraction patterns. SNU-6 exhibits high permanent porosity $(1.05 cm^{3} g^{−1})$ with high Langmuir surface area $(2910 m^{2} g^{−1}).$ It shows high $H_{2}$ gas storage capacity (1.68 wt % at 77 K and 1 atm; 4.87 wt % (excess) and 10.0 wt % (total) at 77 K and 70 bar) with high isosteric heat $(7.74 kJ mol^{−1})$ of $H_{2}$ adsorption as well as high $CO_{2}$ adsorption capability (113.8 wt % at 195 K and 1 atm). Compound 2 undergoes a single-crystal-to-single-crystal transformation on guest exchange with n-hexane to provide $\{[Zn_{2}(BPnDC)_{2}(dabco)]⋅6 (n-hexane)⋅3 H_{2}O\}_{n}$ $(2_{hexane}).$ The transformation involves dynamic motion of the molecular components in the crystal, mainly a bending motion of the square planes of the paddle-wheel units resulting from rotational rearrangement of phenyl rings and carboxylate planes of $BPnDC^{2−}.$
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	29
Volume Number	14
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2008-01-01
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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