Catalyst‐ and Solvent‐Free Synthesis of a Chemically Stable Aza‐Bridged Bis(phenanthroline) Macrocycle‐Linked Covalent Organic Framework

Abstract

Developing new linkage-based covalent organic frameworks (COFs) is one of the major topics in reticular chemistry.E lectrically conductive COFs have enabled applications in energy storage and electrochemical catalysis,w hich are not feasible using insulating COFs.D espite significant advances,t he construction of chemically stable conductive COFs by the formation of new linkages remains relatively unexplored and challenging. Here we report the solvent-and catalyst-free synthesis of at wo-dimensional aza-bridged bis(phenanthroline) macrocycle-linked COF (ABBPM-COF) from the thermally induced poly-condensation of at ri-topic monomer and ammonia gas.The ABBPM-COF structure was elucidated using multiple techniques,i ncluding X-rayd iffraction analysis combined with structural simulation, revealing its crystalline nature with an ABC stackingmode.Further experiments demonstrated its excellent chemical stability in acid/base solutions.E lectrical-conductivity measurements showed that the insulating ABBPM-COF becomes as emiconducting material after exposure to iodine vapor.

Recent Advances in the Synthesis and Applications of Nitrogen-Containing Macrocycles

“…Incorporation of polyaza macrocycles into macrocycle-linked covalent organic frameworks in catalyst and solvent-free conditions resulted in a successful attempt at an electrically conductive material [ 33 ].…”

Metalated covalent organic frameworks: from synthetic strategies to diverse applications

“…Based on the design strategy of modular condensation polymerization, at least 9 kinds of topologies of 2D monolayers, i.e., hcb, 5,52 sql, 53,54 kgm, [55][56][57][58] cem, 59 hxl, 60 cpi, 61 bex, 62,63 kgd, [64][65][66] and tth, 63,66 have been reported by combining more than one organic monomer or making the pore structure dissymmetric via changing the edge lengths and vertex angles. 67 Moreover, the 2D monolayers may adopt different stacking modes in space, e.g., AA, 5 AB, 5,68,69 and ABC, [70][71][72][73][74] further enriching the structural diversity of 2D COFs. Conversely, less than 100 different 3D COFs have been reported since the first report in 2007.…”

“…67 Moreover, the 2D monolayers may adopt different stacking modes in space, e.g. , AA, 5 AB, 5,68,69 and ABC, 70–74 further enriching the structural diversity of 2D COFs. Conversely, less than 100 different 3D COFs have been reported since the first report in 2007.…”

Electroactive Covalent Organic Framework Enabling Photostimulus-Responsive Devices

“…), (200), and (210) crystal facets, respectively. At a higher angle, the peak at 26.7°represents the (001) facet and indicates an interlayer π−π stacking distance of 3.3 Å, which is a reasonable value for π−π stacking systems 54,55. To compare with theoretical PXRD patterns, BDFamide-Tp in eclipsed stacking mode (Figure2c,e) and staggered stacking mode (Figure2d,f) was simulated.…”