Post-Synthetic Mannich Chemistry on Metal-Organic Frameworks: System-Specific Reactivity and Functionality-Triggered Dissolution.
Post-Synthetic Mannich Chemistry on Metal-Organic Frameworks: System-Specific Reactivity and Functionality-Triggered Dissolution.
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DOI：
10.1002/chem.201801419
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发表时间：
2018-08-01
期刊：
影响因子：
--
通讯作者：
Burrows AD
中科院分区：
文献类型：
--
作者：
Amer Hamzah H;Gee WJ;Raithby PR;Teat SJ;Mahon MF;Burrows AD
锆MOF [Zr 6 O 4（OH）4（bdc-NH 2）6]（UiO-66-NH 2，bdc-NH 2 =2-氨基-1，4-苯二甲酸酯）与多聚甲醛和吡唑、咪唑或2-巯基咪唑的曼尼希反应通过C-N键形成导致合成后修饰（PSM）。与咪唑（Him）的反应完成，而与吡唑（Hpyz）和2-巯基咪唑（HimSH）的反应分别得到高达41%和36%的转化率。Mannich产物的BET表面积从UiO-66-NH 2的BET表面积减小，但化合物在273 K下对CO2的吸附选择性比N2高。 含硫醇的MOFs吸附水溶液中的汞离子，去除率高达99%。与吡唑的曼尼希反应在[Zn 4 O（bdc-NH 2）3]（IRMOF-3）上成功，但在[Zn 2（bdc-NH 2）2（dabco）]（dabco= 1，4-二氮杂双环[2.2.2]辛烷）上的类似反应得到[Zn 3（bdc-NH 2）1.32（bdc-NHCH 2 pyz）1.68（dabco）] n2 C7 H8 5，而与咪唑的反应得到预期的PSM产物。化合物5通过溶解-重结晶过程形成，该过程由“游离”吡唑氮原子与dabco竞争与锌（II）中心的配位而触发。 相比之下，咪唑酯上的“游离”氮原子太远而不能以这种方式竞争。[In（OH）（bdc-NH 2）]（MIL-68（In）-NH 2）上的曼尼希反应在第一步后停止，产物被鉴定为[In（OH）（bdc-NH 2）0.41（bdc-NHCH 2 OCH 3）0.30（bdc-N= CH 2）0.29]，杂环的加入被空间相互作用阻止。
The Mannich reaction of the zirconium MOF [Zr6O4(OH)4(bdc‐NH2)6] (UiO‐66‐NH2, bdc‐NH2=2‐amino‐1,4‐benzenedicarboxylate) with paraformaldehyde and pyrazole, imidazole or 2‐mercaptoimidazole led to post‐synthetic modification (PSM) through C−N bond formation. The reaction with imidazole (Him) goes to completion whereas those with pyrazole (Hpyz) and 2‐mercaptoimidazole (HimSH) give up to 41 and 36 % conversion, respectively. The BET surface areas for the Mannich products are reduced from that of UiO‐66‐NH2, but the compounds show enhanced selectivity for adsorption of CO2 over N2 at 273 K. The thiol‐containing MOFs adsorb mercury(II) ions from aqueous solution, removing up to 99 %. The Mannich reaction with pyrazole succeeds on [Zn4O(bdc‐NH2)3] (IRMOF‐3), but a similar reaction on [Zn2(bdc‐NH2)2(dabco)] (dabco=1,4‐diazabicyclo[2.2.2]octane) gave [Zn3(bdc‐NH2)1.32(bdc‐NHCH2pyz)1.68(dabco)]⋅2 C7H8 5, whereas the reaction with imidazole gave the expected PSM product. Compound 5 forms via a dissolution–recrystallisation process that is triggered by the “free” pyrazolate nitrogen atom competing with dabco for coordination to the zinc(II) centre. In contrast, the “free” nitrogen atom on the imidazolate is too far away to compete in this way. Mannich reactions on [In(OH)(bdc‐NH2)] (MIL‐68(In)‐NH2) stop after the first step, and the product was identified as [In(OH)(bdc‐NH2)0.41(bdc‐NHCH2OCH3)0.30(bdc‐N=CH2)0.29], with addition of the heterocycle prevented by steric interactions.
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DOI：
10.1039/c0cc02990d
发表时间：
2010-11-07
期刊：
Chemical communications (Cambridge, England)
影响因子：
--
作者：
Garibay SJ;Cohen SM
通讯作者：
Cohen SM
影响因子：
4.3
作者：
Ameloot, Rob;Aubrey, Michael;Long, Jeffrey R.
通讯作者：
Long, Jeffrey R.
影响因子：
2.3
作者：
Gee, William J.;Batten, Stuart R.
通讯作者：
Batten, Stuart R.
影响因子：
16.6
作者：
Burrows, Andrew D.;Frost, Christopher G.;Richardson, Christopher
通讯作者：
Richardson, Christopher
影响因子：
15
作者：
Cavka, Jasmina Hafizovic;Jakobsen, Soren;Lillerud, Karl Petter
通讯作者：
Lillerud, Karl Petter