2D and 3D Porphyrinic Covalent Organic Frameworks: The Influence of Dimensionality on Functionality

Abstract

The construction of 2D and 3D covalent organic frameworks (COFs) from functional moieties for desired properties has gained much attention. However, the influence of COFs dimensionality on their functionalities, which can further assist in COF design, has never been explored. Now, by selecting designed precursors and topology diagrams, 2D and 3D porphyrinic COFs (2D‐PdPor‐COF and 3D‐PdPor‐COF) are synthesized. By model building and Rietveld refinement of powder X‐ray diffraction, 2D‐PdPor‐COF crystallizes as 2D sheets while 3D‐PdPor‐COF adopts a five‐fold interpenetrated pts topology. Interestingly, compared with 2D‐PdPor‐COF, 3D‐PdPor‐COF showed interesting properties, including 1) higher CO2 adsorption capacity; 2) better photocatalytic performance; and 3) size‐selective photocatalysis. Based on this study, we believe that with the incorporation of functional moieties, the dimensionality of COFs can definitely influence their functionalities.

Three-Dimensional Large-Pore Covalent Organic Framework with stp Topology

“…Covalent organic frameworks (COFs), [1][2][3][4][5] a remarkable class of organic porous crystalline materials with high surface areas and promising stabilities, have attracted wide interests in varied fields including gas adsorption and separation, [6][7][8][9] catalysis, [10][11][12][13][14][15] optoelectronics, [16][17][18][19][20] and some others. [21][22][23][24][25][26] Over the past decade, most researches have been focused on two-dimensional (2D) COFs with eclipsed AA stacking modes. [1][2][3][4] Three-dimensional (3D) COFs are considered as ideal platforms for abundant uses because of their interconnected channels, superior surface areas, and fully exposed active sites.…”

Photocatalytic Oxidation Reactions Mediated by Covalent Organic Frameworks and Related Extended Organic Materials

“…In addition, 2 N , N ′-bicarbazole-based CTFs, BC-CTF , and Ph-BC-CTF, were able to perform the same reaction ( Yan et al, 2019 ). Later on, a 2D and a 3D Pd-containing porphyrinic COFs, 2D-PdPor-COF and 3D-PdPor-CO F, performed in a very efficient manner the oxidation of sulfides ( Meng et al, 2020 ). Furthermore, h-LZU1 , a nanostructured COF, showed a slightly worse recyclability and selectivity in photocatalytic sulfoxidation of organic sulfides ( Liu et al, 2020a ).…”

“…Both oxygen anion radical and singlet oxygen have been found as reactive oxygen species in this process. In addition, Por-sp 2 c-COF (cyanovinylene-based porphyrin-containing COF) was used for the synthesis of imine under photocatalytic conditions ( Yan et al, 2019 ; Meng et al, 2020 ). Moreover, Por-sp 2 c-COF was also employed for the oxidation of secondary amines, using TEMPO as co-Catalyst, allowing the use of red light in a two-photon absorption process ( Shi et al, 2020 ).…”

Visual naked-eye detection of SARS-CoV-2 RNA based on covalent organic framework capsules

“…Covalent organic frameworks (COFs) are an emerging kind of porous crystalline materials with excellent stability, regular porosity, pre-designable structures and customizable functions, making them a perfect candidate for enzyme encapsulation [32] , [33] , [34] , [35] . COFs not only triumph over the defects of poor crystallinity and uneven pore distribution of most inorganic porous materials, but also conquer the deficiency of metal–organic frameworks (MOFs) that easy collapse in water [36] , [37] , [38] . These remarkable physicochemical properties of COFs make them exhibit great potential for biomolecules encapsulation applications.…”