Currently, most organic semiconducting materials (OSMs) are π-conjugated structures in one or two dimension (2D), where the lack of layer-layer π-conjugation connection greatly blocks their electron delocalization and transport. The 3D fully conjugated materials could solve this issue because they can provide efficient charge-transport pathways throughout the whole 3D skeleton, in which the suitable 3D building block is the key to the development of fully conjugated 3D OSMs. Cyclooctatetraene (COT) and its derivatives are good candidates due to their π-conjugation with 3D saddle-shaped architecture. In this Concept, we discuss the key features of saddle-shaped COT-based derivatives and their synthetic strategy, then we present the current development of using the COT derivatives as building blocks to construct the 3D fully conjugated organic small compound- and polymer-based OSMs. The properties and perspectives of these OSMs in photovoltaics, electro-catalysis and electrical conductivities are also discussed. These recent advances in the developing 3D fully conjugated materials could potentially open up a new frontier in the design of OSMs.
Keywords: conjugation; electron delocalization; organic frameworks; organic semiconductors; saddle-shape.
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