Insights on the design and electron-acceptor properties of conjugated organophosphorus materials.

Abstract

The development of conjugated organic materials has become a rapidly evolving field of research, particularly with a view toward practical applications in so-called organic electronics that encompass a variety of device types, such as OLEDs, OPVs, and OFETs. Almost all of these devices minimally require the presence of electron-donor and -acceptor components that act as p- and n-type semiconductors, respectively. Research over the past two decades has shown that while there is an abundant resource of organic p-type materials, suitable n-type species are few and far between. To overcome this severe bottleneck for the further development of organic electronics, researchers have identified organo-main-group avenues as valuable alternatives toward organic electron-acceptor materials that may ultimately be used as n-type components in practical devices. One particular element of interest in this context is phosphorus, which at first glance may not necessarily suggest such properties. In this Account, I provide detailed insights on the origin of the electron-acceptor properties of organophosphorus-based conjugated materials and include an overview of important molecular species that have been developed by my group and others. To this end, I explain that the electron-acceptor properties of conjugated organophosphorus materials originate from an interaction known as negative hyperconjugation. While this particular interaction creates a simply inductively withdrawing phosphoryl substituent for π-conjugated scaffolds, incorporation of a phosphorus atom as an integral part of a cyclic substructure within a π-conjugated system provides a much more complex, versatile, and consequently highly valuable tool for the tuning of the electron-acceptor properties of the materials. Notably, the degree of negative hyperconjugation can effectively be tailored in various ways via simple substitution at the phosphorus center. This is now well established for phosphole-based molecular materials, in which the electron-acceptor properties are also mirrored by the degree of antiaromaticity of the system. Particularly, fused and π-extended phosphole materials show appreciable electron-acceptor properties, evident in low reduction potentials and corresponding LUMO levels. But these features do not always translate into powerful n-type materials. My group and others have thus recently been focusing on molecular organophosphorus scaffolds that also involve incorporation of imino or carbonyl groups, next to the incorporation of low coordinate phosphorus centers, to achieve superior electron-acceptor features. This state-of-the-art research has confirmed the great potential of the organophosphorus route toward powerful electron-acceptor materials, but further work is required to also establish these species as functional n-type materials.