4.8 Article

Robust Supramolecular Nano-Tunnels Built from Molecular Bricks**

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 13, Pages 7148-7154

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202013117

Keywords

aggregation-induced emission; CO2 adsorption; crystal transformations; linear organic salts; porous molecular crystals

Funding

  1. National Natural Science Foundation of China [21788102, 22001006, 81372274, 81501591, 8141101080]
  2. Innovation and Entrepreneurship Project of Overseas Returnees in Anhui Province [2020LCX017]
  3. Research Grants Council of Hong Kong [16308016, C6009-17G, 16305618, 16304819]
  4. Innovation and Technology Commission [ITC-CNERC14SC01]
  5. Oversea Study Program of Guangzhou Elite Project from Guangzhou City, Engineering and Physical Sciences Research Council [EP/N004884/1]
  6. European Research Council under the European Union [321156]
  7. European Research Council (ERC) [321156] Funding Source: European Research Council (ERC)

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The linear ionic molecule reported in this study assembles into a supramolecular nano-tunnel structure through ionic and pi-pi stacking interactions, exhibiting anisotropic guest adsorption behavior. The material shows good thermal and chemical stability, undergoes phase transformations, and displays high CO2/CH4 selectivity. Additionally, the bulk crystals have vapochromic properties due to aggregation-induced emission.
Herein we report a linear ionic molecule that assembles into a supramolecular nano-tunnel structure through synergy of trident-type ionic interactions and pi-pi stacking interactions. The nano-tunnel crystal exhibits anisotropic guest adsorption behavior. The material shows good thermal stability and undergoes multi-stage single-crystal-to-single-crystal phase transformations to a nonporous structure on heating. The material exhibits a remarkable chemical stability under both acidic and basic conditions, which is rarely observed in supramolecular organic frameworks and is often related to structures with designed hydrogen-bonding interactions. Because of the high polarity of the tunnels, this molecular crystal also shows a large CO2-adsorption capacity while excluding other gases at ambient temperature, leading to high CO2/CH4 selectivity. Aggregation-induced emission of the molecules gives the bulk crystals vapochromic properties.

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