The use of molecules bridged between two electrodes as a stable rectifier is an important goal in molecular electronics. Until recently, however, and despite extensive experimental and theoretical work, many aspects of our fundamental understanding and practical challenges have remained unresolved and prevented the realization of such devices. Recent advances in custom-designed molecular systems with rectification ratios exceeding 105 have now made these systems potentially competitive with existing silicon-based devices. Here, we provide an overview and critical analysis of recent progress in molecular rectification within single molecules, self-assembled monolayers, molecular multilayers, heterostructures, and metal-organic frameworks and coordination polymers. Examples of conceptually important and best-performing systems are discussed, alongside their rectification mechanisms. We present an outlook for the field, as well as prospects for the commercialization of molecular rectifiers.
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