Transpositional Circularly Polarized Luminescence from Transient Charge‐Transfer Coassembly

Abstract

Charge‐transfer (CT) complexation between electron‐rich and deficient aromatics has been widely applied in functional optical and photovoltaic materials. The selective complexation and spontaneous disassociation behavior of a dynamic charge‐transfer coassembly possess potential in designing smart and dynamic luminescent materials, which however have not been addressed so far. In this work, the transient charge‐transfer driven coassembly between π‐conjugated amino acids and tetracyanobenzene, showing dynamic luminescent transition and circularly polarized luminescence (CPL) evolution property, is illustrated. Transient coassembly behaviors are independent to the diverse binding sites covering fluorene, naphthalene, and anthracene, attributed to the intramolecular CH…π interaction. Incorporation of fluorescent dyes enables a transient light harvesting process with hyperchromic CPL properties. Spontaneous green‐to‐red CPL transition hydrogels are also fabricated by embedding a competitive CT donor. Using a polymeric matrix treated by organic solvents, charge‐transfer coassembly is immobilized with diverse circularly polarized luminescence. Such sensitive complexation shows applications in moisture‐responsive luminescent materials and multiple luminescent color evolutions are realized.

Modulating the Excited State Chirality of Dynamic Chemical Reactions in Chiral Micelles

“…[6] This strategy even exhibits some better performance, such as excellent generality, enhancing the circular polarization of some CPL-active materials, and so on. [7] In terms of composition, the CPL materials constructed by the self-assembly contain at least two components, emitter and chiral host matrix, such as chiral liquid crystal, [8] chiral gels, [9] chiral polymers, [10] deoxyribonucleic acid (DNA), [11] cyclodextrin [12] and so forth, which possess capacity to endow both chiral and achiral chromophores with controllable CPL activity. [13] In this case, various achiral organic or inorganic emitters could be endowed with CPL activity in recent years.…”

Biomolecule‐Based Circularly Polarized Luminescent Materials: Construction, Progress, and Applications

“…The dissymmetry g‐factor for CPL reached up to ±0.04. They further proposed that the unique property of transient CT complexation and CPL may be helpful for the preparation of spontaneous color and CPL transition materials [32] . The assembly of chiral molecules often relies not only on noncovalent interactions but also a variety of binding modes for chiral induction and transfer [35]…”

Manipulating Supramolecular Chirality and Circularly Polarized Luminescence of Cholesteryl Naphthalimides with Multiple Chiral Domains

“…1−15 Through rational design of building blocks and control of assembly environments, it is possible to control highly ordered arrangement of building blocks to form nanostructures with different dimensions, such as nanofibers (1D), 16,17 semipermeable membranes (2D), 18 and vesicles (3D). 19,20 So far, a variety of building blocks have been developed, such as amino acid derivatives, 21,22 metal complexes, 23 aromatic compounds, 24 fullerenes, proteins, 25 and polyhedral oligosilsesquioxanes (POSSs) 26−28 to construct multifunctional nanomaterials, which have been applied in drug delivery, catalysis, crystal engineering, synthesis of macromolecules, and other fields.…”

“…Supramolecular self-assembly or coassembly, as a common way to construct biological macromolecules, has attracted extensive attention. The supramolecular assembly process is mainly dominated by intermolecular noncovalent weak forces, including π–π stacking, C–H···π, hydrogen-bonding interactions, halogen-bond interactions, metal–ligand coordination, van der Waals force, steric hindrance, CH/HC interactions, and so on. − Through rational design of building blocks and control of assembly environments, it is possible to control highly ordered arrangement of building blocks to form nanostructures with different dimensions, such as nanofibers (1D), , semipermeable membranes (2D), and vesicles (3D). , So far, a variety of building blocks have been developed, such as amino acid derivatives, , metal complexes, aromatic compounds, fullerenes, proteins, and polyhedral oligosilsesquioxanes (POSSs) − to construct multifunctional nanomaterials, which have been applied in drug delivery, catalysis, crystal engineering, synthesis of macromolecules, and other fields.…”