Electrochemically Generated Thin Films of Microporous Polymer Networks: Synthesis, Properties, and Applications

Abstract

Electrochemical oxidative polymerization of rigid, multifunctional monomers allows for the synthesis of microporous thin films with high surface areas. Multifunctional, carbazole‐ and thiophene‐based rigid monomers have been utilized as rigid 3D building blocks (tectons) toward microporous polymer films with relatively smooth surface morphology. Within the last four years, several studies following this approach have been published that report interesting results on the application of these electrogenerated films in organic electronics, photoluminescence‐based or electrochemical chemodetectors, electrochemical supercapacitors, and light‐harvesting antennae for exciton pumping. In this work, the synthetic approaches for the electrochemical polymerization of multifunctional carbazole‐ and thiophene‐based tectons as well as resulting properties and application possibilities of the electrogenerated microporous polymer films are reviewed.

Trends and challenges for microporous polymers

“…Thiophene-and carbazole-based building blocks are therefore interesting choices as these tectons can be electropolymerized to create thin films on electrodes. 56,126 For the first reliable measurements of the surface areas of such films, which is hard to achieve as very low sample masses are naturally obtained, krypton sorption was used to determine a surface area of up to 1300 m 2 g À1 in a carbazole based CMP film, which compares nicely to the surface area found in a related bulk material. 126,127 These values could be even increased applying thiophene based monomers (42000 m 2 g À1 ).…”

“…A review on the generation of thiophene and carbazole-based CMP films prepared by electropolymerization has been published by the Scherf group recently and thus just some highlights in applications of these films are repeated here. 56 Both carbazole and thiophene-based thin films of CMPs have been applied for sensing applications, for example as electrochemical detectors or luminescent sensors for explosive nitroaromatic compounds (e.g. nitrobenzene, dinitrotoluene and trinitrotoluene), showing a significantly increased current response or a quenched luminescence compared to a reference electrode without film deposition.…”

“…Tectons functionalized with thiophene or carbazole moieties can be directly polymerized on electrodes to create compact but still microporous thin films. 56 As polymers of these types (e.g.…”

“…It is not the aim of this review to give a conclusive overview on the whole field of microporous polymers, as excellent reviews on these materials have been published in recent years. [1][2][3]39,40,42,56,57,92,93 On the contrary, we will try to identify some trends and worthwhile research directions within the field of microporous polymers. Within the following chapters we will concentrate on a special structural or functional feature of a certain class of microporous polymers and from there on develop new perspectives on emerging applications.…”

Design of Open‐Shell π‐Conjugated Microporous Polymer Film with Super‐High Conductivity

“…Recently, scientists electrochemically generated thin films of microporous polymer networks. They used multifunctional carbazole‐ and thiophene‐based rigid monomers to build rigid 3D building blocks and obtained microporous polymer films with relatively smooth surface morphology . For example, Jiang and co‐workers designed thiophene‐based building blocks and used electropolymerization to form solution processable conjugated microporous polymer films, which can be used for device fabrications.…”