Zinc Bromide: A General Mediator for the Ionothermal Synthesis of Microporous Polymers via Cyclotrimerization Reactions

Conjugated microporous polymers (CMPs) are porous organic materials that display (semi)conducting behavior due to their highly -conjugated structures, making them promising next-generation materials for applications requiring both electrical conductivity and porosity. Currently, most CMPs and related porous aromatic frameworks (PAFs) are prepared using expensive transition metals (e.g., Pd), significantly increasing the costs associated with their synthesis. Lewis acid-mediated cyclotrimerization reactions of methyl ketones and nitriles represent promising and green alternative methods for CMP and PAF synthesis. Herein, we demonstrate that the generality of the solvent-free cyclotrimerization reactions is significantly improved by using ZnBr2 instead of ZnCl2 as the ionothermal medium. Specifically, we show that 1,4-diacetylbenzene (DAB), 4,4-diacetylbiphenyl (DABP), 2,7-diacetylfluorene (DAF), 1,3,5-triacetylbenzene (TAB), tetrakis(4-acetylphenyl)methane (TAPM), and 1,4-dicyanobenzene (DCNB) can be polymerized in molten ZnBr2 to produce highly conjugated and microporous materials, as confirmed by 77 K N2 adsorption measurements, IR, and solid-state NMR. These findings support that ZnBr2 is an excellent Lewis acid mediator and medium for the ionothermal synthesis of porous organic materials.