Department of Chemistry and Biochemistry, University of Bern , Freiestrasse 3, 3012 Bern, Switzerland.
Swiss Light Source, Paul Scherrer Institute , CH-5232 Villigen, Switzerland.
J Am Chem Soc. 2015 Oct 14;137(40):13072-8. doi: 10.1021/jacs.5b09231. Epub 2015 Oct 2.
A flexible and porous metal-organic framework, based on Co(II) connectors and benzotriazolide-5-carboxylato linkers, is shown to selectively react with guest molecules trapped in the channels during the sample preparation or after an exchange process. Stimulated by a small crystal shrinking, upon compression or cooling, the system undergoes a reversible, nonoxidative nucleophilic addition of the guest molecules to the metal ion. With dimethylformamide, only part of the penta-coordinated Co atoms transform into hexa-coordinated, whereas with the smaller methanol all of them stepwise increase their coordination, preserving the crystallinity of the solid at all stages. This extraordinary example of chemisorption has enormous implications for catalysis, storage, or selective sieving.
一种基于 Co(II)连接物和苯并三唑-5-羧酸盐连接物的灵活多孔金属有机骨架，被证明可以在样品制备过程中或在交换过程后选择性地与被困在通道中的客体分子反应。在小晶体收缩的刺激下，在压缩或冷却时，该体系经历了客体分子对金属离子的可逆、非氧化亲核加成。对于二甲基甲酰胺，只有部分五配位的 Co 原子转化为六配位，而对于较小的甲醇，它们都逐步增加其配位，在所有阶段都保持固体的结晶度。这种化学吸附的非凡例子对催化、储存或选择性筛分具有巨大的意义。
