An Anionic Microporous Polymer Network Prepared by the Polymerization of Weakly Coordinating Anions

Abstract

Organic zeolite: A microporous, covalent organic network with high surface area was synthesized by polymerization of [B(C6F4Br)4]−. The countercations, located within the pore channels, are highly accessible and can be easily exchanged, comparable to the extra‐framework cations in zeolites. In this way a [MnII(bpy)]2+ complex can be synthesized and immobilized in the network.

Trends and challenges for microporous polymers

“…Here, novel permanently ionically charged MPNs are applied, from which the counterions are used directly or after ion exchange as the catalysts, yielding an intriguing intermediate between molecular and solid immobilized catalysts. 76 The latter approach will be described in more detail in a later chapter about the field of permanently charged MPNs. Finally, MPNs have been used as classical supports for the immobilization of metal or metal oxide nanoparticles.…”

Macrocyclic Weakly Coordinating Anions

“…There are also no organic,n anoporous,p olymericW CAs except onep orousf ramework with interconnected perfluorotetraphenylborate building blocks, which was recently synthesized by Thomasa nd co-workers. [34] Matsumi et al synthesized nonporousp olyethers with tetracoordinated Bi nt he polymer chain ( Figure 3, upper left). [35][36][37] Recently Jäkle ad co-workers reported the synthesis of the first weakly coordinating block copolymers, which are nonporous ( Figure 3, upper right).…”

“…[44] The complex has been immobilizedi nz eolitesa nd more recently in anionic microporous polymer (AMP) networks to reduce selfoxidation and dimerization of the catalyst. [34,45] An advantage of the M-WCA overz eolites and AMPs may be the larger pores and the solubility,w hich could simplify immobilization. Compared to AMPs, the crystallinity of M-WCAs could give the complexc ation inside the M-WCA ab etter-defined steric environment, which may have ab eneficial impact on selectivity and product yield.…”

“…Catalyticr eactions with [Mn(bipy) 2 ] 2 + can be carried out under anhydrous conditions below 100 8C. [34] Under such conditions, M-WCAs should be sufficiently stable.…”

“…[8] Recently,the coupling of tetraphenylborate buildingb locks by Sonogashira coupling was demonstrated by Thomas and co-workers,giving evidencet hat anionic organic units can be connected by using organometallic catalysis. [34] If the charge at the substrate is nonetheless aproblem, then the alternative synthesis via neutralm acrocycles (Scheme 2) could be as olution. In this case, the coordination www.chemeurj.org number at Bw ould be increased from three to four only in the last step by using phenylmagnesiumb romide, phenyllithium, or fluoride as reactants.…”