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首页> 外文期刊>Chemistry: A European journal >Post-synthetic modification of Zr-metal-organic frameworks through cycloaddition reactions
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Post-synthetic modification of Zr-metal-organic frameworks through cycloaddition reactions

机译：通过环加成反应对Zr-金属-有机骨架进行后合成修饰

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Cycloaddition reactions are highly attractive for post-synthetic modification of metal-organic frameworks (MOFs). We report herein on cycloaddition reactions with PIZOF(R ~1,R ~2)s, which are porous interpenetrated Zr-based MOFs with Zr _6O _4(OH) _4(CO _2) _(12) as the nodes and the dicarboxylates ~-O _2C[PE-P(R ~1,R ~2)-EP]CO _2 ~- (P: phenylene, E: ethynylene; R ~1, R ~2: side chains at the central phenylene unit) as the linkers. 1,3-Dipolar cycloaddition between the pendant ethyne moieties of PIZOF(OMe,OCH _2C≡CH) and 4-methylbenzyl azide resulted in 98 % conversion of the ethyne groups. Reactions of PIZOF(OMe,O(CH _2) _3furan) with maleimide, N-methylmaleimide, and N-phenylmaleimide converted 98, 99, and 89 % of the furan moieties into the Diels-Alder adducts. However, no reaction occurred with maleic anhydride. High-resolution ~1H NMR spectra were crucial in determining the conversion and identifying the reaction products. Of all the reagents (NaOD/D _2O, D _2SO _4, Bu 4NF, CsF, CsF/DCl, and KHF _2) tested for the disassembly of the PIZOFs in [D _6]DMSO, the combination of CsF and DCl was found to be the best. The disassembly at room temperature was fast (5-15 min), and after the addition of K _2CO _3 the ~1H NMR data were identical to those of the diacids (=protonated linkers) dissolved in pure DMSO. This allowed for simple structure elucidation through data comparison. CsF/DCl dissolves not only PIZOFs but also the hydrolytically very stable UiO-66.
机译：环加成反应对于金属有机骨架（MOF）的合成后修饰非常有吸引力。我们在此报告PIZOF（R〜1，R〜2）s的环加成反应，PIZOF（R〜1，R〜2）是Zr _6O _4（OH）_4（CO _2）_（12）为结点且二羧酸盐〜 -O _2C [PE-P（R〜1，R〜2）-EP] CO _2〜-（P：亚苯基，E：亚乙炔基; R〜1，R〜2：中心亚苯基单元的侧链）连接器。 PIZOF（OMe，OCH_2C≡CH）的乙炔侧基与4-甲基苄基叠氮化物之间的1,3-偶极环加成反应导致乙炔基团的转化率为98％。 PIZOF（OMe，O（CH _2）_3呋喃）与马来酰亚胺，N-甲基马来酰亚胺和N-苯基马来酰亚胺的反应将98％，99％和89％的呋喃部分转化为Diels-Alder加合物。但是，与马来酸酐没有反应发生。高分辨率〜1H NMR光谱对于确定转化率和确定反应产物至关重要。在[D _6] DMSO中检测到的PIZOF拆卸的所有试剂（NaOD / D _2O，D _2SO _4，Bu 4NF，CsF，CsF / DCl和KHF _2）中，发现CsF和DCl的组合做最好的。在室温下快速分解（5-15分钟），加入K _2CO _3后，〜1H NMR数据与溶于纯DMSO的二元酸（质子化连接子）相同。这样可以通过数据比较来简化结构说明。 CsF / DCl不仅溶解PIZOF，而且溶解非常水解的UiO-66。

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