The syntheses, characterization, and emission properties of three tetragonal prismatic cages, 4a-4c, constructed from eight 90° Pt(II) acceptors, four linear dipyridyl ligands, and two tetraphenylethene (TPE)-based sodium benzoate ligands, are described. These cages are emissive in dilute solutions due to the metal-coordination-induced partial restriction of intramolecular rotation of their TPE units, while the dipyridyl moieties, which act as the pillars as well as the solvents, strongly influence these emissions. Specifically, cages 4a and 4b, bearing a 4,4'-dipyridine and a 1,2-di(4-pyridyl)ethylene as their pillar parts, respectively, display good emissions in common organic solvents at 485-493 nm that are derived from the TPE units. In contrast, cage 4c, with its BODIPY-based dipyridyl unit, exhibits two emission bands at 462-473 and 540-545 nm, originating from the TPE and BODIPY fluorophores, respectively. Moreover, cage 4b has been employed as a turn-on fluorescent sensor for thiol-containing amino acids via a self-destructive reaction, while the cage can also be regenerated via the addition of Pt(II) acceptors. The studies described herein not only enrich the ongoing research on fluorescent materials but also pave the way to prepare stimuli-responsive supramolecular coordination complexes.
Herein, we report the preparation of a multifunctional metallacage-core supramolecular gel by orthogonal metal coordination and host-guest interactions. A tetragonal prismatic cage with four appended 21-crown-7 (21C7) moieties in its pillar parts was first prepared via the metal-coordination-driven self-assembly of cis-Pt(PEt)(OTf), tetraphenylethene (TPE)-based sodium benzoate ligands and linear dipyridyl ligands. Further addition of a bisammonium linker to the cage delivered a supramolecular polymer network via the host-guest interactions between the 21C7 moieties and ammonium salts, which formed a supramolecular gel at relatively higher concentrations. Due to the incorporation of a TPE derivative as the fluorophore, the gel shows emission properties. Multiple stimuli responsiveness and good self-healing properties were also observed because of the dynamic metal coordination and host-guest interactions used to stabilize the whole network structure. Moreover, the storage and loss moduli of the gel are 10-fold those of the gel without the metallacage cores, indicating that the rigid metallacage plays a significant role in enhancing the stiffness of the gel. The studies described herein not only enrich the functionalization of fluorescent metallacages via elegant ligand design but also provide a way to prepare stimuli-responsive and self-healing supramolecular gels as robust and smart materials.
Control over the fluorescence of supramolecular assemblies is crucial for the development of chemosensors and light-emitting materials. Consequently, the postsynthetic modification of supramolecular structures via host-guest interactions has emerged as an efficient strategy in recent years that allows the facile tuning of the photophysical properties without requiring a tedious chemical synthesis. Herein, we used a phenanthrene-21-crown-7 (P21C7)-based 60° diplatinum(II) acceptor 8 in the construction of three exohedral P21C7 functionalized rhomboidal metallacycles 1-3 which display orange, cyan, and green emission colors, respectively. Although these colors originate from the dipyridyl precursors 10-12, containing triphenylamine-, tetraphenylethene-, and pyrene-based fluorophores, respectively, the metal-ligand coordination strongly influences their emission properties. The metallacycles were further linked into emissive supramolecular oligomers by the addition of a fluorescent bis-ammonium linker 4 that forms complementary host-guest interactions with the pendant P21C7 units. Notably, the final ensemble derived from a 1:1 mixture of 1 and 4 displays a concentration-dependent emission. At low concentration, i.e., <25 µM, it emits a blue color, whereas an orange emission was observed when the concentration exceeds >5 mM. Moreover, white-light emission was observed from the same sample at a concentration of 29 µM, representing a pathway to construct supramolecular assemblies with tunable fluorescence properties.
Selenium is a semimetallic element lying in group XVI of the periodic table with its chemical properties resembling sulfur. But owing to its relatively low electronegativity and large atomic radius compared with sulfur, selenium also shows unique properties. This feature endows selenium-containing compounds with high reactivity and sensitivity. Although organic selenium chemistry has been developing very fast, the successful introduction of selenium into polymer science is rather scarce. Fortunately, we have seen a drastic rising trend in the area of selenium-containing polymers over the past decade. In this Perspective, the synthetic routes of selenium-containing polymers are summarized, and their unique stimuli-responsive properties are elaborated on, together with their diverse applications in the field of adaptive and biomedical materials.
The dynamic Lewis multicore system (DLMCS) which integrates the Lewis acidic boron center(s) and an ammonium salt in one molecule has shown good catalytic performance in polymer synthesis. Inspired by the insightful intramolecular ammonium cation assisted mechanism, herein, we communicated a superior organoboron system by replacing a nitrogen atom with a phosphorus atom. The upgraded mono-, di-, and trinuclear organoboron catalysts show significantly improved catalytic performance and heat resistance for versatile epoxideinvolved transformations, including ring-opening copolymerization of epoxides and cyclic anhydrides, copolymerization of CO 2 and epoxides, and ring-opening polymerization of epoxides. 11 B NMR, single-crystal X-ray diffraction, and DFT results imply that the replacing nitrogen with phosphorus in an onium cation led to an effective epoxide activation and nucleophilic attack of the counterion on the activated epoxide, which remarkably shortened the initiation period and accelerated chain expansion, resulting in the obvious improvement of the activity. The upgraded phosphonium-containing organoboron system combined with the mechanism study and insightful understanding would be instructive in designing advanced metal-free catalysts.
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