Core-Substituted Naphthalene-Diimides (cNDI) and Related Derivatives: Versatile Scaffold for Supramolecular Assembly and Functional Materials

Abstract

Naphthalene-diimide (NDI) derived building blocks have been explored extensively for supramolecular assembly as they exhibit attractive photophysical properties, suitable for applications in organic optoelectronics. Core-substituted derivatives of the NDI chromophore (cNDI) differ significantly from the parent NDI dye in terms of optical and redox properties. Adequate molecular engineering opportunities and substitution-dependent tunable optoelectronic properties make cNDI derivatives highly promising candidates for supramolecular assembly and functional material. This short review discusses recent development in the area of functional supramolecular assemblies based on cNDIs and related molecules.

Synthesis, Photophysical Properties and Self‐Assembly of a Tetraphenylethylene‐Naphthalene Diimide Donor‐Acceptor Molecule

“…[15] Strategic functionalization at the NDI core enhances their self-assembly properties both in solution and in the solid state. [16] The choice of solvent also plays a crucial role in designing molecular scaffolds. [15,16] In this regard, tetraphenylethylene (TPE) molecules have garnered attention due to their aggregation-induced emission (AIE) properties, [17] proving vital for solid-state emission.…”

Spatiotemporal dynamics of supramolecular polymers by in situ quantitative catalyst-free hydroamination

“…This atom-economical hydroamination of NDIs possesses unique characteristics that are distinctively different from other existing chemical reactions for π-systems: (1) various amines, many of which are commercially available, are applicable to functionalize the π-systems, and thus (2) the π-conjugated structure is changed by the reaction to exhibit remarkable changes in the optical and electronic properties. In this context, considering that NDIs have been widely known as building blocks of supramolecular polymers, 42–45 we conceived that our catalyst-free hydroamination of NDIs could be used as a new family of in situ reactions to trigger macroscopic changes of supramolecular polymers based on NDI molecules using various amines. The in situ reaction of π-conjugated molecules within supramolecular polymers is also expected to exhibit characteristic reactivity different from that in homogeneous monodisperse solutions, because the molecules are pre-organized and locally condensed.…”

Synthesis, optical properties and cation mediated tuning of the reduction potentials of core-annulated naphthalene diimide derivatives

“…One of the attractive methods developed in recent years to modify the parent NDI is its lateral expansion or core annulation, 14 which led to derivatives with adjustable electrochemical and optical properties. 5 In core annulation, there occurs a decrease in the band gap and a bathochromic shift of the absorption maxima, which often reach the near infra-red (NIR) region.…”

“…Core annulation is also accompanied by an enhanced intermolecular overlap of the π-systems in the bulk, leading to improved electronic coupling between functional components. 14 Annulation with a heterocyclic ring gives additional room for alteration of the properties via interactions with cations. Therefore, synthesis of a core-annulated NDI-based ligand would be a clever approach to generate a diverse range of properties in the presence of various cations, without doing substantial synthetic modifications.…”