Color-Tunable Binary Copolymers Manipulated by Intramolecular Aggregation and Hydrogen Bonding.

Construction of color-tunable luminescent polymeric materials with enhanced emission intensity and room-temperature phosphorescence (RTP) performance regulated by a single chromophore component is highly desirable in the scope of photoluminescent materials. Herein, a set of binary copolymers were facilely synthesized using free radical polymerization by selecting different types of polymer matrix and N-substituted naphthalimides (NPA) as chromophores. Surprisingly, the fluorescence emission of copolymers could be remarkably enhanced, because of the intramolecular aggregation of NPA manipulated by a single polymer chain in both solution and solid state. Moreover, RTP signals of binary copolymers were all clearly observed in the air without any processing procedure, because of the embedding of phosphors into hydrogen bonding networks after copolymerization with vinyl-based acrylamide monomers. Taking advantages of the synergistic effect of copolymerization-induced aggregation and copolymerization-induced rigidification to promote optical performance, UV stimulus-responsive luminescent polymer films with processability, flexibility, and adjustable emission wavelength were simply prepared using a drop-casting method in large scale, the setting of which is the basis for application in the fields of organic optoelectronics, information security, and bioimaging/sensing.

Tale of COF-on-MOF Composites with Structural Regulation and Stepwise Luminescence Enhancement.

Integrating metal-organic framework (MOF)-covalent organic framework (COF) allows versatile engineering of hybrid materials with properties superior to pristine components, especially COFs suffered from aggregation-caused quenching (ACQ), unlocking more possibilities to improve the luminescence of COFs. In this work, we prepared various MOF@COF composites with different COF layer thicknesses, in which stable UiO-66-NH2 served as the inner substrate and 1,3,5-benzenetricarboxaldehyde (BT), and 3,3'-dihydroxybenzidine (DH) were used to construct a COF layer. In addition to the conventional preparation method, we increased the ratio of BT and DH to be 1:2.5, and impressively, the morphologies of acquired UC (1:2.5) materials were quite different from the previous reticular structure and gradually extended from the spherical structure to the prickly structure with the increase of COF monomers. Remarkably, all of the UC materials possessed better luminescence properties than individual COF due to the limited COF layers. Meanwhile, UC-1 materials with an optimal COF layer displayed the strongest emission. In comparison with a single COF, the quantum yields of UC-1 and UC-1 (1:2.5) were increased nearly 7 times and 5 times, respectively. Moreover, the fluorescence of UC-1 materials was progressively enhanced via selective F- sensing. This work is expected to shed light on the potential hybridization of MOF-COF with structural adjustment, morphological design, and luminescence enhancement.

Tunable fluorescence emission based on multi-layered MOF-on-MOF.

Luminescent metal-organic frameworks (MOFs) have garnered considerable attention in various fields. Herein, we proposed a hierarchical confinement strategy based on MOF-on-MOF to tune luminescence emission ranging from blue to red including white light in a flexible way. The easily available ZIF-8 MOF was used as a host for the confinement of two kinds of size-matching dyes (perylene and rhodamine B) to obtain a layered ZIF-8@dye@ZIF-8@dye via in situ encapsulation and seed-mediated synthesis. ZIF-8@dye@ZIF-8@dye materials with different fluorescence emission in dispersed and solid states were both obtained by tuning the initial encapsulation concentration of dye and changing the structure of the inner and outer ZIF-8@dye layers. To our delight, ZIF-8@0.125perylene@ZIF-8@25RhB with white light emission in the dispersed state was obtained; meanwhile, ZIF-8@0.125perylene + 25RhB and mechanically mixed ZIF-8@0.125perylene + ZIF-8@25RhB could not realize white light emission under the same conditions, indicating that the proposed hierarchical confinement strategy facilitated white light regulation. Similarly, the emission of ZIF-8@dye@ZIF-8@dye in the solid state has also been investigated; ZIF-8@perylene@ZIF-8@3RhB with white light emission was obtained, while white light emission could not be achieved in ZIF-8@perylene + 3RhB and ZIF-8@perylene + ZIF-8@3RhB, which further indicated the importance of the hierarchical confinement strategy based on MOF-on-MOF. The proposed hierarchical confinement strategy may also inspire the development of other functional optical MOF materials.

Construction and Sensing Amplification of Raspberry-Shaped MOF@MOF.

MOFs@MOFs (metal-organic frameworks, MOFs) possess precise customized functionalities and predesigned structures that enable the implementation of structure and property regulation for specific functions in comparison to traditional single MOFs. However, the synthesis and fluorescence properties of multilayer MOFs@MOFs are still worth improving. Herein, a fluorescent raspberry-shaped MOF@MOF was constructed via optimized seed-mediated synthesis by tuning the reaction time, reaction mode, and reaction concentration, involving the initial synthesis of the UiO-66-NH2 core and then the coating of the UiO-67-bpy shell. The raspberry-shaped UiO-66@67-bpy showed stable fluorescence and desirable sensing selectivity for the Hg2+ ion under the interference of other ions; meanwhile, the raspberry-shaped UiO-66@67-bpy indicated amplified sensing performance than pure UiO-66-NH2, mechanically mixed UiO-66-NH2 + UiO-67-bpy, and UiO-66@UiO-67 counterpart due to the accumulation effect of outer UiO-67-bpy toward Hg2+. Density functional theory (DFT) calculations including adsorption energy calculations and electronic density difference analysis further showed that the enhanced fluorescence quenching was possibly attributed to the outer UiO-67-bpy enrichment promoting the charge transfer between Hg2+ and the ligands of fluorescent UiO-66@67-bpy. The synergistic effect of MOFs@MOFs unlocks more possibilities for the construction of enhanced sensors and other applications.

Supramolecular Engineering of Efficient Artificial Light-Harvesting Systems from Cyanovinylene Chromophores and Pillar[5]arene-Based Polymer Hosts.

Enhanced emission and adjustable wavelength for single luminogen systems are highly desirable in the scope of photoluminescent materials. Herein, a supramolecular strategy has been proposed for supramolecular assembly-induced enhanced emission and valid emission manipulation by fabricating an amphiphilic copolymer host material with pillar[5]arene units as the side chains, whereby cyanovinylene-based (CV) derivatives are anchored to the polymer hosts via host-guest interactions. The guest-bearing copolymers can further form luminescent supramolecular polymer nanoparticles (SPNs). Remarkably, the as-prepared SPNs exhibit dramatic emission enhancement and tunable fluorescence wavelength, ascribing to the synergetic effects involving the restriction of intramolecular motions and the prevented excimer formation for CV moieties, as endowed by host-guest interactions and the entanglement of the polymer chains. Furthermore, the SPNs can be established as efficient artificial light-harvesting systems via the inclusion of Nile red into the particles for broadened emission spectra. As a proof-of-concept study, the use of pillar[5]arene-containing polymer hosts largely facilitates the emission enhancement and wavelength adjustment for the inherent luminogens, setting the basis for the supramolecular design of highly tunable luminescent systems.

Efficient Aggregation-Induced Emission Manipulated by Polymer Host Materials.

Linear copolymer hosts bearing a number of pillar[5]arene dangling side chains are synthesized for the facile construction of highly emissive supramolecular polymer networks (SPNs) upon noncovalently cross-linking with a series of tetraphenyethylene (TPE)-based tetratopic guests terminated with different functional groups through supramolecular host-guest interactions. An extremely high fluorescence quantum yield (98.22%) of the SPNs materials is obtained in tetrahydrofuran (THF) by fine-tuning the parameters, and meanwhile supramolecular light-harvesting systems based on spherical supramolecular nanoparticles are constructed by interweaving 9,10-distyrylanthracene (DSA) and TPE-based guest molecules of aggregation-induced emission (AIE) with the copolymer hosts in the mixed solvent of THF/H2 O. The present study not only illustrates the restriction of the intramolecular rotations (RIR)-ruled emission enhancement mechanism regulated particularly by macrocyclic arene-containing copolymer hosts, but also suggests a new self-assembly approach to construct high-performance light-harvesting materials.