Yingzhi Jin

Near-infrared (NIR) organic materials are of great importance for both fundamental research and practical applications. While much effort has been taken to covalently design and synthesize NIR organic materials with a low energy gap, there are supramolecular approaches for tuning the energy gap to noncovalently fabricate NIR organic assemblies and materials. In this concept article, we summarize and discuss several supramolecular approaches, including the fabrication of charge transfer supramolecular complexes, the fabrication of supramolecular J-aggregates, and the fabrication of supramolecularly stabilized organic radicals. The nature of noncovalent interactions in supramolecular approaches can provide NIR organic assemblies and materials with unique properties such as reversibility, stimuli-responsiveness, recyclability, and adaptive abilities.

Supramolecular approaches for the fabrication of NIR organic assemblies and materials are discussed and highlighted. These include the fabrication of charge transfer supramolecular complexes, the fabrication of supramolecular J-aggregates, and the fabrication of supramolecularly stabilized organic radicals, which display unique properties such as reversibility, stimuli-responsiveness, recyclability and adaptive abilities.

Supramolecular chemistry provides a tool for the formation of highly ordered structures by means of noncovalent interactions. Soft supramolecular nanoparticles are self-assembled nanoassemblies based on small building blocks and stabilized by basic noncovalent interactions, selective host–guest interactions, or a combination of different interaction types. This review provides an overview of the existing approaches for the formation of supramolecular nanoparticles by various types of noncovalent interactions, with a strong focus on host–guest-mediated assemblies. The approaches are ordered based on the nature of the stabilizing supramolecular interaction, while focusing on the aspects that determine the particle structure. Where applicable, the use of these self-assembled nanostructures as vectors in molecular diagnostics and therapeutics is described as well. The stable yet reversible nature of supramolecular interactions and their chemical flexibility offer great prospects for the development of highly engineered nanoparticles which are compatible with the complexity of living systems.

Soft supramolecular nanoparticles (SNPs) are formed by building blocks that are brought together by multiple noncovalent supramolecular interactions. SNPs are stable yet reversible three-dimensional assemblies, and can be used for a variety of applications. This review summarizes the existing approaches for the formation of soft SNPs and focuses on their potential biomedical applications.

Improved understanding of the underwater attachment strategy of the blue mussels and other marine organisms has inspired researchers to find new routes to advanced materials. Mussels use polyphenols, such as the catechol-containing amino acid 3,4-dihydroxyphenylalanine (DOPA), to attach to surfaces. Catechols and their analogues can undergo both oxidative covalent cross-linking under alkaline conditions and take part in coordination chemistry. The former has resulted in the widespread use of polydopamine and related materials. The latter is emerging as a tool to make self-healing materials due to the reversible nature of coordination bonds. We review how mussel-inspired materials have been made with a focus on the less developed use of metal coordination and illustrate how this chemistry can be widely to make self-healing materials.

Inspired by nature: The ability of blue mussels and other marine creatures to attach to surfaces underwater and to make advanced materials have gained increasing awareness and interest amongst chemists. The combination of catechols and coordination chemistry to yield self-healing materials is the most recent sprout on this growing tree and is the focus of this Minireview.

The self-assembly of small organic molecules interacting via non-covalent forces is a viable approach towards the construction of highly ordered nanostructured materials. Among various molecular components, natural and unnatural nucleobases can undergo non-covalent self-association to form supramolecular architectures with ad hoc structural motifs. Such structures, when decorated with appropriate electrically/optically active units, can be used as scaffolds to locate such units in pre-determined positions in 2D on a surface, thereby paving the way towards a wide range of applications, e.g., in optoelectronics. This review discusses some of the basic concepts of the supramolecular engineering of natural and unnatural nucleobases and derivatives thereof as well as self-assembly processes on conductive solid substrates, as investigated by scanning tunnelling microscopy in ultra-high vacuum and at the solid/liquid interface. By unravelling the structure and dynamics of these self-assembled architectures with a sub-nanometer resolution, a greater control over the formation of increasingly sophisticated functional systems is achieved. The ability to understand and predict how nucleobases interact, both among themselves as well as with other molecules, is extremely important, since it provides access to ever more complex DNA- and RNA-based nanostructures and nanomaterials as key components in nanomechanical devices.

Recent progress in supramolecular engineering of the self-assembly of natural and unnatural nucleobases on various conducting solid substrates, as investigated by scanning tunnelling microscopy (STM) operating under UHV conditions and at the solid/liquid interfaces, is reviewed comprehensively.