A Series of Layered Assemblies of Hydrogen-Bonded, Hexagonal Networks of C3-Symmetric π-Conjugated Molecules: A Potential Motif of Porous Organic Materials

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• 作者：Ichiro Hisaki ; Shoichi Nakagawa ; Nobuaki Ikenaka ; Yutaka Imamura ; Michio Katouda ; Motomichi Tashiro ; Hiromu Tsuchida ; Tomoki Ogoshi ; Hiroyasu Sato ; Norimitsu Tohnai ; Mikiji Miyata
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：May 25, 2016
• 年：2016
• 卷：138
• 期：20
• 页码：6617-6628
• 全文大小：1202K
• 年卷期：0
• ISSN：1520-5126

文摘

Hydrogen-bonded porous organic crystals are promising candidates for functional organic materials due to their easy construction and flexibility arising from reversible bond formation–dissociation. However, it still remains challenging to form porous materials with void spaces that are well-controlled in size, shape, and multiplicity because even well-designed porous frameworks often fail to generate pores within the crystal due to unexpected disruption of hydrogen bonding networks or interpenetration of the frameworks. Herein, we demonstrate that a series of C₃-symmetric π-conjugated planar molecules (Tp, T12, T18, and Ex) with three 4,4′-dicarboxy-o-terphenyl moieties in their periphery can form robust hydrogen-bonded hexagonal networks (H-HexNets) with dual or triple pores and that the H-HexNets stack without interpenetration to yield a layered assembly of H-HexNet (LA-H-HexNet) with accessible volumes up to 59%. Specifically, LA-H-HexNets of Tp and T12 exhibit high crystallinity and permanent porosity after desolvation (activation): SA_BET = 788 and 557 m² g^–1, respectively, based on CO₂ sorption at 195 K. We believe that the present design principle can be applied to construct a wide range of two-dimensional noncovalent organic frameworks (2D-nCOFs) and create a pathway to the development of a new class of highly porous functional materials.