This feature article reviews research of core-substituted naphthalenediimides (cNDIs) in a comprehensive yet easily readable manner. Their synthesis, electrochemistry and spectroscopy are covered first with emphasis on the ability of cNDIs with electron donating substituents to absorb and fluoresce in all colors without global structural changes and cNDIs with electron withdrawing substituents to reach unprecedented extents of π-acidity. The section on supramolecular chemistry covers face-to-face π-stacks and peripheral hydrogen bonds, that on molecular recognition moves from pH and fluoride sensors to the binding to telomeric DNA in vivo and intercalation into π-stacks and sticky tweezers. cNDIs can recognize and transport anions by functional anion–π interactions. The section on electron transport describes cNDIs as air-stable n-semiconductors with high charge mobility and use as OFETs. Photoinduced electron transport by rainbow cNDIs has been used for the creation of artificial photosystems in solution, in bilayer membranes and on solid substrates. Examples include multicolor light harvesting architectures, organic solar cells, photosystems that can open up into ion channels, and supramolecular n/p-heterojunctions with antiparallel redox gradients. The review is highly interdisciplinary but should appeal most to organic, biosupramolecular and physical chemists.

Halogen‐ and chalcogen‐based σ‐hole interactions have recently received increased interest in non‐covalent organocatalysis. However, the closely related pnictogen bonds have been neglected. In this study, we introduce conceptually simple, neutral, and monodentate pnictogen‐bonding catalysts. Solution and in silico binding studies, together with high catalytic activity in chloride abstraction reactions, yield compelling evidence for operational pnictogen bonds. The depth of the σ holes is easily varied with different substituents. Comparison with homologous halogen‐ and chalcogen‐bonding catalysts shows an increase in activity from main group VII to V and from row 3 to 5 in the periodic table. Pnictogen bonds from antimony thus emerged as by far the best among the elements covered, a finding that provides most intriguing perspectives for future applications in catalysis and beyond.

This critical review covers progress with synthetic transport systems, particularly ion channels and pores, between January 2006 and December 2009 in a comprehensive manner. This is the third part of a series launched in the year 2000, covering a rich collection of structural and functional motifs that should appeal to a broad audience of non-specialists, including to organic, biological, supramolecular and polymer chemists. Impressive breakthroughs have been achieved over the past four years in part because of a fruitful expansion toward new types of interactions, including metal–organic, π–π, aromatic electron donor–acceptor, anion–π or anion–macrodipole interactions as well as dynamic covalent bonds (169 references).

This review summarizes the use of orthogonal dynamic covalent bonds to build functional systems. Dynamic covalent bonds are unique because of their dual nature. They can be as labile as non-covalent interactions or as permanent as covalent bonds, depending on conditions. Examples from nature, reaching from the role of disulfides in protein folding to thioester exchange in polyketide biosynthesis, indicate how dynamic covalent bonds are best used in functional systems. Several synthetic functional systems that employ a single type of dynamic covalent bonds have been reported. Considering that most functional systems make simultaneous use of several types of non-covalent interactions together, one would expect the literature to contain many examples in which different types of dynamic covalent bonds are similarly used in tandem. However, the incorporation of orthogonal dynamic covalent bonds into functional systems is a surprisingly rare and recent development. This review summarizes the available material comprehensively, covering a remarkably diverse collection of functions. However, probably more revealing than the specific functions addressed is that the questions asked are consistently quite unusual, very demanding and highly original, focusing on molecular systems that can self-sort, self-heal, adapt, exchange, replicate, transcribe, or even walk and “think” (logic gates). This focus on adventurous chemistry off the beaten track supports the promise that with orthogonal dynamic covalent bonds we can ask questions that otherwise cannot be asked. The broad range of functions and concepts covered should appeal to the supramolecular organic chemist but also to the broader community.