Full-Color Circularly Polarized Luminescence of Supramolecular Polymers with Handedness Inversion Regulated by Anion and Temperature

Abstract

Constructing full-color circularly polarized luminescence (CPL) materials with switchable handedness in the solid state is an appealing yet considerably challenging task, especially for supramolecular polymer films assembled from homochiral monomers. Herein, supramolecular polymers with full-color CPL and inverted handedness are realized through the coassembly of a homochiral cholesterol derivative (PVPCC), metal ions (Zn 2+ ), and achiral fluorescent dyes. The obtained coassembled systems show anion-directed supramolecular chirality inversion by exchanging the anions of NO 3 − , ClO 4 − , BF 4 − , and Cl − . For instance, the negative CD and right-handed CPL are detected in the PVPCC/Zn(NO 3 ) 2 aggregates, which convert into positive CD and left-handed CPL after introducing Cl − , corresponding to the transformation from nanorods to nanofibers. Furthermore, the tunable CPL color and handedness inversion of the coassembly system of PVPCC/Zn(NO 3 ) 2 and achiral fluorescent dyes can be established by alternately changing the assembling temperature of 298 and 273 K. Importantly, the full-color CPL polymeric materials are then constructed by doping the PVPCC/Zn(NO 3 ) 2 /dyes complexes into poly(methyl methacrylate) (PMMA) film, which maintains the handedness inversion and shows the enhanced CPL performance. The work not only deepens the understanding of chirality inversion in supramolecular chemistry but also helps to construct full-color CPL materials with switchable handedness from homochiral building blocks in materials science.

Dynamic Circularly Polarized Luminescence Switching of Metal–Organic Supramolecular Polymers Directed by the Competition of Solvent-Assisted Nucleation and Thermal Nucleation

“…According to different assembly mechanisms, supramolecular polymerization is usually divided into ring–chain, isodesmic and cooperative polymerization. , As ring–chain and isodesmic polymerization are greatly limited by the few molecular building blocks, most supramolecular polymers mainly adopt a cooperative supramolecular polymerization model. Usually, the cooperative supramolecular polymerization involves two processes of nucleation and elongation, and parameters like temperature, , solvent, − and sonication , often play important roles in the nucleation process and greatly affect the subsequent elongation process with tunable chirality transfer. If we can gain more insights into the nucleation pathway, it is promising to deeper the understanding of the chiral transfer rule in various chemical assembly systems, especially for the ubiquitous ones with a cooperative assembly mechanism.…”

Achiral substituent- and stoichiometry-controlled inversion of supramolecular chirality and circularly polarized luminescence in ternary co-assemblies

“…6–9 One of the pivotal issues in supramolecular chirality is controlled chiral inversion. 10–15 This can be achieved by various external stimuli such as temperature, 16 solvents, 17 light, 18 metal ions, 19 pH, 20 and redox. 21 However, most of the reported supramolecular chirality inversions have focused on single-component self-assembled systems, 22–25 and both basic and application research studies of multiple-component co-assemblies with controllable chirality are still limited.…”

Iridium(iii)-catalyzed one-pot synthesis of planar chiral emissive materials through C–H activation

“…5 In many functional applications, CPL-active materials are highly coveted by researchers for their versatile applications in optical information storage, 6,7 asymmetric catalysis, 8 3D display, 9 anti-counterfeiting, 10 and various other specialized fields. 11–17 At present, many mature strategies have been developed for constructing CPL-active materials through [2.2]paracyclophane frameworks, 18,19 such as directly covalent bonding with chromophores, 20,21 utilizing through-space electron transfer to construct D–A systems, 22 and constructing fused ring conjugated systems. 23–28 However, these molecules were mostly obtained by multistep synthesis and tedious purification procedures, which precluded their scalability and further applications.…”