Shivanna Mohana, Zheng Jia-Jia, Ray Keith G, Lto Sho, Ashitani Hirotaka, Kubota Yoshiki, Kawaguchi Shogo, Stavila Vitalie, Yao Ming-Shui, Fujikawa Takao, Otake Ken-Ichi, Kitagawa Susumu
Institute for Integrated Cell-Material Sciences, Kyoto University Institute for Advanced Study, Kyoto University, Yoshida Ushinomiya-cho, Sakyo-ku, Kyoto, 606-8501, Japan.
Laboratory of Theoretical and Computational Nanoscience, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Chinese Academy of Sciences, No. 11 ZhongGuanCun BeiYiTiao, Beijing, 100190, P. R. China.
Commun Chem. 2023 Apr 4;6(1):62. doi: 10.1038/s42004-023-00853-1.
Incorporating strong electron donor functionality into flexible coordination networks is intriguing for sorption applications due to a built-in mechanism for electron-withdrawing guests. Here we report a 2D flexible porous coordination network, [Ni(4,4'-bipyridine)(VTTF)]n(1) (where HVTTF = 2,2'-[1,2-bis(4-benzoic acid)-1,2ethanediylidene]bis-1,3-benzodithiole), which exhibits large structural deformation from the as-synthesized or open phase (1α) into the closed phase (1β) after guest removal, as demonstrated by X-ray and electron diffraction. Interestingly, upon exposure to electron-withdrawing species, 1β reversibly undergoes guest accommodation transitions; 1α⊃O (90 K) and 1α⊃NO (185 K). Moreover, the 1β phase showed exclusive O sorption over other gases (N, Ar, and CO) at 120 K. The phase transformations between the 1α and 1β phases under these gases were carefully investigated by in-situ X-ray diffraction, in-situ spectroscopic studies, and DFT calculations, validating that the unusual sorption was attributed to the combination of flexible frameworks and VTTF (electron-donor) that induces strong interactions with electron-withdrawing species.
由于存在一种用于吸电子客体的内在机制，将强电子供体功能引入柔性配位网络对于吸附应用而言颇具吸引力。在此，我们报道了一种二维柔性多孔配位网络，[Ni(4,4'-联吡啶)(VTTF)]n(1)（其中HVTTF = 2,2'-[1,2-双(4-苯甲酸)-1,2-亚乙基]双-1,3-苯并二硫醇），经X射线和电子衍射表明，该网络在客体去除后会从合成态或开放相(1α)转变为封闭相(1β)，呈现出较大的结构变形。有趣的是，在暴露于吸电子物种时，1β会可逆地发生客体容纳转变；1α⊃O（90 K）和1α⊃NO（185 K）。此外，1β相在120 K时对其他气体（N、Ar和CO）表现出对O的专属吸附。通过原位X射线衍射、原位光谱研究和密度泛函理论计算仔细研究了这些气体下1α和1β相之间的相变，证实这种异常吸附归因于柔性框架和VTTF（电子供体）的组合，其与吸电子物种产生强烈相互作用。
