The construction and application of fullerene-containing pillar[n]arene organic-inorganic hybrid composites/systems has been discussed and summarized. Both supramolecular interactions and covalent bonds were involved during the preparation process. By using supramolecular interactions, pillar[n]arenes mainly donate the hydrophobic and electron-rich cavity for complexing fullerene and its derivatives. The "bigger-sized" unmodified pillar[10]arene could directly include C60 in a stoichiometry of 1/1 via host-guest interaction, while the perfunctionalized "smaller-sized" pillar[5]arene with an enlarged channel-like structure could further interact with "size-fixed" fullerene. Additionally, recognition site-containing modified fullerene could integrate with the pillararene cavity for fabricating the functional supramolecular system, which could be further used for applications in photodevices. By forming stable covalent bonds, coupled pillar[n]arene and fullerene hybrid composites could be synthesized via either the modification of pillar[n]arenes with the fullerene subunits, or the utilization of fullerene as the partial structural skeleton for building pillar[n]arenes, in which diverse classic organic synthesis reactions were involved. Interestingly, those fullerene-containing pillar[n]arenes with free cavities could further participate in the formation of hierarchical architectures, such as mechanically interlocked molecules, by cooperating with the "dumbbell" molecule.
Abstract Room temperature phosphorescent (RTP) materials have triggered wide interests because of their excellent performance and various promising applications. However, conventional RTP materials possessing color‐tunable and ultralong afterglow often suffer from low phosphorescent emission efficiency. Herein, a long lifetime and high‐efficiency RTP emission system composed of boric acid as the host matrix and organic phosphors as guest molecules is constructed by suppressing the non‐radiative transition process and promoting the triplet exciton of the phosphors. The synergistic effect of the physically limited domain and supramolecular anchoring also contributes to the ultralong lifetime (up to 1.85 s) and high phosphorescence quantum yield (up to 53%). The afterglow can be visually observed for 30 s. With a large overlap of π ‐conjugated chromophores, the emission peak of RTP redshifted, realizing cyan, green, and red afterglow in the monochromatic domain. In addition, the emission of colorful afterglow and white afterglow is adjustable with the different co‐doping ratios. Finally, the application of RTP materials to anti‐counterfeiting encryption is demonstrated.
The investigation of ferroelectric materials is an important aspect of condensed matter physics. Compared to the traditional inorganic ferroelectric ones, organic ferroelectric materials possess unique advantages, including light weight, scalability, flexibility, and solvent treatability. However, the study of organic ferroelectric materials is still in its infancy, especially from the view of supramolecular chemistry; various mechanisms of forming self-assembly and thus diverse building blocks employed are not yet to be further developed. Herein, a pillararene-based charge transfer (CT) self-assembly was produced by utilizing pillar[5]quinone (P5Q) as the electron acceptor and phenothiazine (PTZ) as the electron donor. Compared to the intrinsic P5Q, our fabricated donor–acceptor complex displays particular intriguing features, such as the enhanced second-harmonic generation and ferroelectric responses, benefiting from the CT interaction between P5Q and PTZ. The current work provides a unique strategy for the successful construction of supramolecular ferroelectrics.
The development of active water oxidation catalysts for water splitting has stimulated considerable interest. Herein, the design and building of single atom Co sites using a supramolecular tailoring strategy are reported, that is, the introduction of pillar[4]arene[1]quinone (P4A1Q) permits mononuclear Co species stereoelectronically assembled on MoS 2 matrix to construct an atomically dispersed MoS 2 @Co catalyst with modulated local electronic structure, definite chemical environment and enhanced oxygen evolution reaction performance. Theoretical calculations indicate that immsobilized single‐Co sites exhibit an optimized adsorption capability of oxygen‐containing intermediates, endowing the catalyst an excellent electrocatalytic oxygen evolution reaction activity, with a low overpotential of 370 mV at 10 mA cm −2 and a small Tafel slope of 90 mV dec −1 . The extendable potential of this strategy to other electrocatalysts such as MoS 2 @Ni and MoS 2 @Zn, and other applications such as the hydrogen evolution reaction was also demonstrated. This study affords new insights into the rational design of single metal atom systems with enhanced electrocatalytic performance.
Citric acid (CA)-based polymeric adsorbent materials were fully characterized and analyzed for the adsorption treatment of methylene blue (MB). Also, the effects of various factors on their performance were thoroughly examined.
The calixarene-based ligand—4-tert-butylsulfonylcalix[4]arene has the capacity of coordinating with various metal cations either individually by itself or together with various carboxylate/thiol-containing coligands. Interestingly, different types of metal cations, various counterions and variable solvents not only generated diverse coordinated cages with special morphology and topology, but also provided a tool in controlling their various porosities, hierarchical architectures, and physiochemical properties. Particularly, those calixarene-based coordinated cages with different porous structures, properly sized hierarchical cage/cavity-like spaces, as well as selected active elemental components greatly promoted applications to electrocatalytic reactions such as hydrogen evolution reaction, oxygen evolution reaction and oxygen reduction reaction. In this chapter, we not only summarized and discussed the preparation of calixarene-based coordinated cages and their applications to electrocatalysis, but also provided academic and industrial concerns and suggestions in future researches.
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