Abstract

Microporous organic polymer networks with weakly coordinating cations in their backbone have been synthesised by metal catalysed C–C bond forming reactions.

Highlights

  • Several classes of these materials, which are built by polymerisation of rigid, two or three dimensional organic tectons have been described such as polymers of intrinsic microporosity (PIMs),[8] covalent organic frameworks (COFs, CTFs)[9,10,11] and conjugated microporous polymers (CMPs).[12,13]

  • We reported the use of tetrakis(4-bromo, 2,3,5,6-tetra uorophenyl)borate as a tecton to generate a microporous anionic borate network (ABN) by Sonogashira–Hagihara coupling with 1,3,5-triethynylbenzene as comonomer.[33]

  • We present the synthesis of two charged co-polymer networks containing a positively charged tetrahedral monomer, i.e. tetraphenylphosphonium and a neutral comonomer

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Summary

Introduction

Microporous polymer networks are of increasing interest regarding their potential applications e.g. in the areas of separation, catalysis and gas storage.[1,2,3,4,5,6,7] Several classes of these materials, which are built by polymerisation of rigid, two or three dimensional organic tectons have been described such as polymers of intrinsic microporosity (PIMs),[8] covalent organic frameworks (COFs, CTFs)[9,10,11] and conjugated microporous polymers (CMPs).[12,13] Depending on the functional groups of the tecton different polymerisation reactions have been described to build such networks, such as oxidative polymerisations,[5,14] polycondensations[15] and trimerisations[16,17] as well as Sonogashira,[12,18,19] Suzuki[20,21] or Yamamoto[22,23] metal-catalysed C–C coupling reactions.Some microporous polymer networks show exceptionally high surface areas which allow the storage of high amounts of gases such as hydrogen or carbon dioxide.[19,24,25] For example tectons based on tetraphenylmethane subunits exhibit BET surface areas of up to 5640 m2 gÀ1.23 Related tetrahedral tectons were reported, using silicon or germanium as central atom to connect the four phenyl rings.[26,27,28,29,30,31] Beside group 14 elements, the exchange of the central carbon with elements from group 13 or 15 should yield negatively or positively charged tectons. The rst group reporting a charged microporous polymer network aTechnische Universitat Berlin, Functional Materials, Hardenbergstr.

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