Matic Ebba S, Bernard Maylis, Jernstedt Alexandra J, Grommet Angela B
Department of Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96, Gothenburg, Sweden.
Ecole Supérieure de Chimie Organique et Minérale, 60200, Compiègne, France.
Chemistry. 2024 Dec 18;30(71):e202403411. doi: 10.1002/chem.202403411. Epub 2024 Nov 7.
Coordination cages and their encapsulated cargo can be manoeuvred between immiscible liquid layers in a process referred to as phase transfer. Among the stimuli reported to drive phase transfer, counterion exchange is the most widespread. This method exploits the principle that counterions contribute strongly to the solubility preferences of coordination cages, and involves exchanging hydrophilic and hydrophobic counterions. Nevertheless, phase transfer of anionic cages remains relatively unexplored, as does selective phase transfer of individual cages from mixtures. Here we compare the phase transfer behaviour of two Fe L cages with the same size and geometry, but with opposite charges. As such, this study presents a rare example wherein an anionic cage undergoes phase transfer upon countercation exchange. We then combine these two cages, and demonstrate that their quantitative separation can be achieved by inducing selective phase transfer of either cage. These results represent unprecedented control over the movement of coordination cages between different physical compartments and are anticipated to inform the development of next-generation supramolecular systems.
配位笼及其封装的客体可以在不混溶的液层之间进行操纵，这个过程称为相转移。在据报道能驱动相转移的刺激因素中，反离子交换最为普遍。该方法利用了反离子对配位笼的溶解度偏好有很大影响这一原理，涉及亲水性和疏水性反离子的交换。然而，阴离子笼的相转移以及从混合物中选择性地进行单个笼的相转移仍相对未被探索。在这里，我们比较了两个尺寸和几何形状相同但电荷相反的铁配体笼的相转移行为。因此，本研究提供了一个罕见的例子，即阴离子笼在反阳离子交换时发生相转移。然后我们将这两个笼结合起来，并证明通过诱导任一笼的选择性相转移可以实现它们的定量分离。这些结果代表了对配位笼在不同物理隔室之间移动的前所未有的控制，并有望为下一代超分子系统的发展提供信息。
