Covalent Organic Framework (COF‐1) under High Pressure. (2nd December 2019)

• Record Type: Journal Article
• Authors: Sun, Jinhua; Iakunkov, Artem; Baburin, Igor A.; Joseph, Boby; Palermo, Vincenzo; Talyzin, Alexandr V.
• Is Part Of: Angewandte Chemie. Volume 132:Number 3(2020)
• Page Start: 1103
• Page End: 1108
• Publication Date: 2019-12-02
• Subjects: 2D-Materialien -- Dichtefunktionalrechnungen -- Hochdruck -- Raman-Spektroskopie -- Röntgenbeugung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201907689
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: COF‐1 has a structure with rigid 2D layers composed of benzene and B3 O3 rings and weak van der Waals bonding between the layers. The as‐synthesized COF‐1 structure contains pores occupied by solvent molecules. A high surface area empty‐pore structure is obtained after vacuum annealing. High‐pressure XRD and Raman experiments with mesitylene‐filled (COF‐1‐M) and empty‐pore COF‐1 demonstrate partial amorphization and collapse of the framework structure above 12–15 GPa. The ambient pressure structure of COF‐1‐M can be reversibly recovered after compression up to 10–15 GPa. Remarkable stability of highly porous COF‐1 structure at pressures at least up to 10 GPa is found even for the empty‐pore structure. The bulk modulus of the COF‐1 structure (11.2(5) GPa) and linear incompressibilities ( k [100] =111(5) GPa, k [001] =15.0(5) GPa) were evaluated from the analysis of XRD data and cross‐checked against first‐principles calculations. Abstract : Synchrotron‐basierte Röntgenbeugung und Raman‐Spektroskopie an COF‐1 mit Mesitylen‐gefüllten und mit leeren Poren bei hohem Druck demonstrieren die Stabilität der Struktur bei bis zu 12–15 GPa. Partielles Amorphisieren und ein Kollabieren des Gerüstes werden bei höherem Druck beobachtet. Experimenteller Kompressionsmodul und lineare Inkompressibilitäten von COF‐1 sind nützlich zur Bewertung theoretischer Beschreibungen von Van‐der‐Waals‐Wechselwirkungen in Festkörpern.