The mechanochemical Scholl reaction as a versatile synthesis tool for the solvent-free generation of microporous polymers

Abstract

<p>Herein we report the mechanochemical Scholl polymerization of 1,3,5-triphenylbenzene in a high speed ball mill.</p>

Beyond the Scholl reaction – one-step planarization and edge chlorination of nanographenes by mechanochemistry

“…Building on this work, we combined the method using FeCl 3 with the planarization to HBC that we described in previous works. 11,22 With this one-pot reaction, we were able to halve the number of required reaction steps and prepare edgechlorinated HBC directly from the dendritic, nonplanar and commercially readily available 5. In the course of this reaction, we were able to obtain 4 in a reaction time of only one hour, while the substitution was driven to completeness by increasing the reaction time and perchlorinated HBC could be successfully prepared.…”

“…Ball milling has established itself as a powerful tool, offering at least as much exibility as solvent-based processes. [12][13][14][15][16] For many elds spanning everything from material synthesis, [17][18][19][20][21][22] main group chemistry 23,24 to organic chemistry, [25][26][27][28] fullerene chemistry 29,30 and lately polymer chemistry, 31 solvent-free pathways have been developed in ball mills. We recently reported on the planarization of nanographenes using mechanochemistry.…”

The mechanochemical Friedel‐Crafts polymerization as a solvent‐free cross‐linking approach toward microporous polymers

“…Of particular interest in this regard is the origin of porosity, which our group recently investigated exemplified by the mechanochemical Scholl polymerization of 1,3,5‐triphenylbenzene (TPB) 60 . Throughout this reaction, the release of HCl was accompanied by a 12 bar pressure increase inside the milling vessel, which was determined by means of a gas pressure and temperature measurement (GTM) system.…”

Benzene Ring Knitting Achieved by Ambient‐Temperature Dehalogenation via Mechanochemical Ullmann‐Type Reductive Coupling

“…[ 40 ] A mechanochemical Scholl reaction of dendritic oligophenylene precursors was reported to afford benchmark nanographenes such as hexa–peri–hexabenzocoronene, triangular shaped C 60 and expanded C 222 under solvent‐free conditions promoted by FeCl 3 , [ 43 ] which was further extended to the Scholl coupling of 1,3,5‐triphenylbenzene. [ 44 ] For the current mechanochemical Scholl coupling‐based pathways, only electron‐rich aromatic building blocks were efficiently polymerized. To extend the monomer scope to electron‐deficient counterparts (e.g., aromatic halides), mechanochemical Ullmann‐type homocoupling of the building block would be a useful complementary pathway, which has not been realized up to now.…”