Asgari Darosch, Grüneberg Julia, Luo Yunkai, Küçükkeçeci Hüseyin, Ghosh Samrat, Chevelkov Veniamin, Fischer-Lang Sabrina, Roeser Jérôme, Lange Adam, Dunn Bruce, Gradzielski Michael, Thomas Arne
Institute of Chemistry, Technische Universität Berlin, Berlin, 10623, Germany.
Department of Materials Science and Engineering, University of California, Los Angeles, CA, 90095, USA.
Nat Commun. 2024 Aug 15;15(1):7031. doi: 10.1038/s41467-024-50953-2.
Non-covalent interactions play an important role for the framework formation of two-dimensional covalent organic frameworks. Until now, π-π interactions and hydrogen bonding are the main reported forces facilitating the stacking of framework layers. Here, we present a two-dimensional anionic covalent organic framework based on tetratopic borate linkages, where layers are connected by ionic interactions between the linkage site and counter cations. The crystalline covalent organic framework is accessed through the formation of an amorphous borate-based polymer and subsequent solvothermal treatment. The progress of crystallization is investigated, revealing the crystallite growth and morphological change from agglomerated dense particles to hollow crystallite spheres. Due to the pillared nature, the crystallites can be exfoliated into nanosheets by sonication of the material in the presence of methanol. The crystallization and ordered arrangement of the lithium ions in the interlayer space is shown to benefit the conductivity tenfold compared to the amorphous material.
非共价相互作用在二维共价有机框架的骨架形成中起着重要作用。到目前为止，π-π相互作用和氢键是促进框架层堆叠的主要报道作用力。在此，我们展示了一种基于四配位硼酸酯连接的二维阴离子共价有机框架，其中各层通过连接位点与抗衡阳离子之间的离子相互作用相连。通过形成无定形硼酸基聚合物并随后进行溶剂热处理来制备结晶共价有机框架。研究了结晶过程，揭示了微晶的生长以及从团聚致密颗粒到空心微晶球的形态变化。由于具有柱状结构，通过在甲醇存在下对材料进行超声处理，微晶可以剥离成纳米片。结果表明，与无定形材料相比，锂离子在层间空间的结晶和有序排列使电导率提高了十倍。
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