Highly ordered organic crystalline materials provide an ideal platform for next-generation flexible electronics.

Constructing multicolor photoluminescent materials with tunable properties is an attractive research objective on account of their abundant applications in materials science and biomedical engineering. By comparison with covalent synthesis, supramolecular chemistry has provided a more competitive and promising strategy for the production of organic materials and the regulation of their photophysical properties. By taking advantage of dynamic and reversible noncovalent bonding interactions, supramolecular strategies can, not only simplify the design and fabrication of organic materials, but can also endow them with dynamic reversibility and stimuli responsiveness, making it much easier to adjust the superstructures and properties of the materials. Occasionally, it is possible to introduce emergent properties into these materials, which are absent in their precursor compounds, broadening their potential applications. In an attempt to highlight the state‐of‐the‐art noncovalent strategies available for the construction of smart luminescent materials, an overview of color‐tunable materials is presented in this Review, with the emphasis being placed on the examples drawn from host–guest complexes, supramolecular assemblies and crystalline materials. The noncovalent synthesis of room‐temperature phosphorescent materials and the modulation of their luminescent properties are also described. Finally, future directions and scientific challenges in the emergent field of color‐tunable supramolecular emissive materials are discussed.

Two-photon excited near-infrared fluorescence materials have garnered considerable attention because of their superior optical penetration, higher spatial resolution, and lower optical scattering compared with other optical materials. Herein, a convenient and efficient supramolecular approach is used to synthesize a two-photon excited near-infrared emissive co-crystalline material. A naphthalenediimide-based triangular macrocycle and coronene form selectively two co-crystals. The triangle-shaped co-crystal emits deep-red fluorescence, while the quadrangle-shaped co-crystal displays deep-red and near-infrared emission centered on 668 nm, which represents a 162 nm red-shift compared with its precursors. Benefiting from intermolecular charge transfer interactions, the two co-crystals possess higher calculated two-photon absorption cross-sections than those of their individual constituents. Their two-photon absorption bands reach into the NIR-II region of the electromagnetic spectrum. The quadrangle-shaped co-crystal constitutes a unique material that exhibits two-photon absorption and near-infrared emission simultaneously. This co-crystallization strategy holds considerable promise for the future design and synthesis of more advanced optical materials.