Rational tuning of binding properties of pillar [5] arene-based sensing material by synergistic effect and its application for fluorescent turn-on detection of isoniazid and controlled reversible morphology.

Isoniazid (INH) is crucial in the treatment of tuberculosis; however, its overuse may induce significant gastrointestinal and hepatic side effects. On October 27, 2017, the International Agency for Research on Cancer, under the auspices of the World Health Organization, published a list of carcinogens for preliminary collation and reference. Isoniazid was categorized as a Group 3 carcinogen. The efficient detection of INH poses an important and challenging task. In this study, a "synergistic effect" is incorporated into the pillar (Yamagishi and Ogoshi, 2018) [5] arene-based macrocyclic host (DPA) by strategically attaching bis-p-hydroxybenzoic acid groups to the opposite ends of the pillar (Yamagishi and Ogoshi, 2018) [5] arene. This combination endows DPA with a reversible and selective fluorescence response to isoniazid. Additionally, DPA exhibits excellent analytical capabilities for isoniazid, including speed and selectivity, with a detection limit as low as 4.85 nM. Concurrently, DPA can self-assemble into a microsphere structure, which is convertible into micrometer-sized tubular structures through host-guest interactions with isoniazid. The introduction of a competitive guest, trimethylamine, enables the reversion to its microsphere structure. Consequently, this study presents an innovative and straightforward synthetic approach for smart materials that facilitates the reversible morphological transition between microspheres and microtubes in response to external chemical stimuli. This discovery provides a valuable strategy for designing "synergistic effects" in constructing trace-level isoniazid-responsive interfaces, with potential applications across various fields, such as controlled drug delivery.

Clamparene: Synthesis, Structure, and Its Application in Spontaneous Formation of 3D Porous Crystals.

Macrocyclic arenes have emerged as pivotal scaffolds in supramolecular chemistry. Despite their significant contributions to molecular recognition and diverse applications, challenges persist in the development of macrocyclic arene-based crystalline materials, particularly in achieving porosity and addressing limitations in adsorption efficiency resulting from the small cavity sizes of existing macrocyclic arenes. In this study, we present the design and synthesis of a novel macrocyclic arene, clamparene (CLP), featuring a rigid backbone, easy synthesis, and a sizable cavity. CLP self-assembles into one-dimensional sub-nanotubes that further organize into a three-dimensional porous framework in the solid state. The crystalline solid of CLP exhibits potential as a porous crystalline adsorbent for various benzene-based contaminants with rapid adsorption kinetics, large uptake amounts, and good recyclability.

A Two-Step Fluorescence-Resonance Energy Transfer System Constructed by Platinum(II) Metallacycle Based Molecular Recognition.

Considerable progress in the construction of efficient fluorescence-resonance energy transfer (FRET) systems has promoted the development of artificial energy transfer materials. However, despite recent advances, the exploration of efficient and easy strategies to fabricate novel supramolecular systems with FRET activities is still a challenge. Here, we report that a two-step FRET system was successfully achieved, driven by platinum metallacycle based host-guest interactions. The two-step FRET system is used for the preparation of a white-light-emitting diode and serves as a nanoreactor for the photosynthetic process. This work offers a strategy for the fabrication of FRET systems and opens opportunities for functional materials constructed by platinum(II) metallacycle based host-guest interactions.

Platinum Metallacycle-Based Molecular Recognition: Establishment and Application in Spontaneous Formation of a [2]Rotaxane with Light-Harvesting Property.

Macrocyclic molecule-based host-guest systems, which provide contributions for the design and construction of functional supramolecular structures, have gained increasing attention in recent years. In particular, platinum(II) metallacycle-based host-guest systems provide opportunities for chemical scientists to prepare novel materials with various functions and structures due to the well-defined shapes and cavity sizes of platinum(II) metallacycles. However, the research on platinum(II) metallacycle-based host-guest systems has been given little attention. In this article, we demonstrate the host-guest complexation between a platinum(II) metallacycle and a polycyclic aromatic hydrocarbon molecule, naphthalene. Taking advantage of metallacycle-based host-guest interactions and the dynamic property of reversible Pt coordination bonds, a [2]rotaxane is efficiently prepared by employing a template-directed clipping procedure. The [2]rotaxane is further applied to the fabrication of an efficient light-harvesting system with multi-step energy transfer process. This work comprises an important supplement to macrocycle-based host-guest systems and demonstrates a strategy for efficient production of well-defined mechanically interlocked molecules with practical values.

Efficient detection of L-aspartic acid and L-glutamic acid by self-assembled fluorescent microparticles with AIE and FRET activities.

Amino acids play an important role in the formation of proteins, enzymes, hormones and peptides in animals. Moreover, aspartic acid and glutamic acid have a critical impact on the central nervous system as excitatory neurotransmitters. Here, we report the highly selective detection of L-glutamic acid (L-Glu) and L-aspartic acid (L-Asp) using fluorescent microparticles constructed by the combination of aggregation-induced emission and self-assembly-induced Förster resonance energy transfer.

Pillar[5]arene-based supramolecular pseudorotaxane polymer material for ultra-sensitive detection of Fe3+ and F.

Recent advancements in ultra-sensitive detection, particularly the Aggregation Induced Emission (AIE) materials, have demonstrated a promising detection method due to their low cost, real-time detection, and simplicity of operation. Here, coumarin functionalized pillar[5]arene (P5C) and bis-bromohexyl pillar[5]arene (DP5) were successfully combined to create a linear AIE supramolecular pseudorotaxane polymer (PCDP-G). The use of PCDP-G as a supramolecular AIE polymer material for recyclable ultra-sensitive Fe3+ and F- detection is an interesting application of the materials. According to measurements, the low detection limits of PCDP-G for Fe3+ and F- are 4.16 × 10-10 M and 6.8 × 10-10 M, respectively. The PCDP-G is also a very effective logic gate and a material for luminous displays.

Ion recognition properties of 2,2'-bibenzimidazole regulated by ammonium-modified pillar[5]arenes.

With the increasing issues of environmental degradation and health problem, the selective detection of toxic ions has attracted considerable attention from researchers. Chemical fluorescent sensors with the advantages of facile operation, high sensitivity, rapid response, and easy visualization are emerging as powerful detection tools towards ions. However, the selective recognition of ions is always hindered by the presence of other interfering substances. Herein, we show that supramolecular host-guest interaction based on a pillar[5]arene provides a new opportunity to regulate the ionic recognition properties of guest molecules. A pillar[5]arene-based host-guest complex HG was constructed through the host-guest interaction between ammonium functionalized pillar[5]arene (HAP5) and 2,2'-bibenzimidazole (G). The host-gust complex HG can realize the successive, highly selective, and sensitive detection of specific ions. It was found that only in the presence of HAP5, the sensitivity towards cations was evidently enhanced, and selective successive recognition for I- and HSO4- was achieved. Those results indicate that the introduction of HAP5 can effectively improve the ion recognition performance of 2,2'-bibenzimidazole, so it is a feasible strategy using supramolecular host-guest interaction to regulate the ionic recognition properties of guest molecules.

A pillar[5]arene-based planar chiral charge-transfer dye with enhanced circularly polarized luminescence and multiple responsive chiroptical changes.

The fabrication of circularly polarized luminescent (CPL) organic dyes based on macrocyclic architecture has become an importantly studied topic in recent years because it is of great importance to both chiral science and supramolecular chemistry, where pillar[n]arenes are emerging as a promising class of planar chiral macrocyclic hosts for CPL. We herein synthesized an unusual planar chiral charge-transfer dye (P5BB) by covalent coupling of triarylborane (Ar3B) as an electron acceptor to parent pillar[5]arene as an electron donor. The intramolecular charge transfer (ICT) nature of P5BB not only caused a thermally responsive emission but also boosted the luminescence dissymmetry factor (g lum). Interestingly, the specific binding of fluoride ions changed the photophysical properties of P5BB, including absorption, fluorescence, circular dichroism (CD), and CPL, which could be exploited as an optical probe for multi-channel detection of fluoride ions. Furthermore, the chiroptical changes were observed upon addition of 1,4-dibromobutane as an achiral guest.

Fluorinated leaning pillar[6]arene: synthesis, structure and selective iodide anion binding by anion-π interactions.

Anion recognition has continuously attracted significant attention due to its important role in environmental and biological sciences. Here, we have designed and synthesized an electron-deficient fluorinated leaning pillar[6]arene 1 that contains two tetrafluoro-benzene units. The electron-deficient fluorinated leaning pillar[6]arene 1 is capable of selectively recognizing iodide anions to form a host-guest complex with 1 : 1 stoichiometry driven by anion-π interactions. Our work ascribes this selective recognition to the preorganization of macrocycles, suitable cavity size, and the effect of anion-π interactions. The innovative application of this macrocycle offers us a new avenue for the design of selective receptors for anions and electron-deficient macrocyclic arenes.

Detection of Aliphatic Aldehydes by a Pillar[5]arene-based Fluorescent Supramolecular Polymer with Vaporchromic Behavior.

The detection of volatile aliphatic aldehydes is of significance because of their chemical toxicity, physical volatility and widespread applications in chemical industrial processes. In this work, the direct detection of aliphatic aldehydes is tackled using a pillar[5]arene-based fluorescent supramolecular polymer with vaporchromic behavior. Thin films with strong orange-yellow fluorescence are prepared by coating the linear supramolecular polymer on glass sheets. When the thin films are exposed to aliphatic aldehydes with different carbon chain lengths, they can selectively sensing n-butyraldehyde (C4 ) and caprylicaldehyde (C8 ), accompanied by fluorescence quenching, indicating that the supramolecular polymer is a highly selective vapochromic response material for aliphatic aldehydes with long alkyl chains.

Pillararenes: fascinating planar chiral macrocyclic arenes.

Chiral macrocycles possess significant value in chiral science and supramolecular chemistry. Pillararenes, as a class of relatively young supramolecular macrocyclic hosts, have been widely used for host-guest recognition and self-assembly. Since the position of substituents on the benzene rings breaks the molecular symmetry (symmetric plane and symmetric center), pillararenes possess planar chirality. However, it is a great challenge to synthesize stable and resolvable enantiomers because of the easy rotation of the phenylene group. In this review, we summarize the construction methods of resolvable chiral pillararenes. We also focus on their applications in enantioselective recognition, chiral switches, chirality sensing, asymmetric catalysis, circularly polarized luminescence, metal-organic frameworks, and highly permeable membranes. Finally, we discuss the future research perspectives in this field of pillararene-based planar chiral materials. We hope that this review will encourage more researchers to work in this exciting field.

A simple pillar[5]arene assembled multi-functional material with ultrasensitive sensing, self-healing, conductivity and host-guest stimuli-responsive properties.

Multi-functional materials have received wide attention due to their potential applications in various fields; therefore, developing a simple and easy strategy for the preparation of multi-functional materials is an interesting issue. In this work, a novel supramolecular gel, TP-QG, has been successfully constructed via the assembly of a simple methoxyl-pillar[5]arene host (TP) and a tripodal (tri-pyridine-4-yl)-amido-benzene guest (Q). Interestingly, TP-QG could act as a multi-functional material and showed strong fluorescence, good self-healing, host-guest stimuli-responsiveness and conductive properties. Due to these properties, TP-QG shows a fascinating application prospect. For instance, TP-QG could exhibit ultrasensitive fluorescence response for Fe3+ and F- in water via the fluorescence "ON-OFF-ON" pathway; the lowest detection limit (LOD) of TP-QG for Fe3+ was 2.32 × 10-10 M and the LOD of TP-QG-Fe for F- was 4.30 × 10-8 M. These properties permit TP-QG to act as not only a Fe3+ and F- sensor, but also an "ON-OFF-ON" fluorescence display material and an efficient logic gate. Meanwhile, the xerogel of TP-QG could remove Fe3+ from water, and the adsorption ratio was 98.68%; the xerogel of TP-QG-Fe could also remove F- from water; the removal ratio was about 87.92%. This work provides a feasible way to construct multi-functional smart materials by host-guest assembly.

In situ formation of Hg2+-coordinated fluorescent nanoparticles through a supramolecular polymer network used for efficient Hg2+ sensing and separation.

There have been many new methods for synthesizing novel nanomaterials with unique functions. Herein, a novel strategy to form fluorescent nanoparticles in situ has been developed, and it can be applied to efficiently sense Hg2+ in living cells and also separate Hg2+ from water.

Theoretical and Experimental Insights into the Self-Assembly and Ion Response Mechanisms of Tripodal Quinolinamido-Based Supramolecular Organogels.

The exploration and understanding of self-assembly and stimuli-responsive mechanisms of supramolecular systems are of fundamental importance for researchers to plan syntheses reasonably. Herein, the self-assembly and ions responsive mechanisms of a tripodal quinolinamido-based supramolecular organogel (TBT-gel) were investigated through experiments and theoretical calculations including independent gradient model (IGM), localized orbitals locator (LOL) and hole-electron theory. According to these studies, the self-assembly mechanism of TBT-gel was based on strong threefold H-bonding and π-π interactions, which induced the TBT forming helical, one-dimensional supramolecular polymer. After addition of Fe3+ into the TBT-gel, the one-dimensional supramolecular polymer had been crosslinked by the Fe3+ through coordination interaction and formed a metallogel (TBT-Fe-gel). Interestingly, the TBT-gel showed selective fluorescent response for Fe3+ and F- based on a competitive coordination mechanism. Moreover, the study on fluorescence responsive mechanism of TBT-gel for Fe3+ and F- implied the ICT mode governs both the electron excitation and de-excitation processes. The calculated results were in agreement with the corresponding experimental results. Notably, the quantum chemical calculations provided a deep understanding and visualized presentation of the assembly and stimuli-responsive mechanisms.

Linear tri-pillar[5]arene-based acceptor for efficiently separate paraquat from water through collaboration effect.

Paraquat, one of non-selective herbicides, is widely used in agricultural production. However, it can cause death of people or animals quickly owing to its fatal toxicity. In the present work, for efficient separation and removal of the paraquat, a concept "employ collaboration effect to enhance the Host-Guest interactions" was rationally introduced into the design of paraquat adsorbent material. According to this concept, a novel linear tri-pillar[5]arene-based acceptor molecule was synthesized. Interestingly, the acceptor shows outstanding adsorption properties for paraquat through the collaboration effect of the adjacent pillar[5]arene moieties in the linear tri-pillar[5]arene acceptor. Compared with other adsorbents such as activated carbon and single-pillar[5]arene-based adsorbent materials, the linear tri-pillar[5]arene acceptor shows higher adsorption rate for paraquat. Additionally, the linear tri-pillar[5]arene acceptor was applied to adsorb the commercial pesticide paraquat sample in water with adsorption rate of 98%. Therefore, the linear tri-pillar[5]arene acceptor could serve as a paraquat adsorbent material and convey greatly potential application in the field of removal of paraquat. The concept "employ collaboration effect to enhance the Host-Guest interactions" is a useful way for the development of adsorption materials.

Pillararene-based AIEgens: research progress and appealing applications.

As a photophysical phenomenon, aggregation-induced emission (AIE) was proposed by Tang in 2001. Due to their excellent fluorescence emission performance, AIEgens and AIE-based fluorescence materials have shown great application potential in a wide range of science fields. Hence, exploring new AIEgens and construction of novel AIE materials are especially vital. In addition, as a new class of macrocyclic hosts, pillararenes have shown excellent performance in supramolecular chemistry. Interestingly, pillararenes also exhibited fairly bright application prospects in the AIE area: firstly, some research studies suggested that pillararenes could serve as a novel AIEgen with considerable fluorescence emission in the aggregated state; moreover, they could also participate in the construction of AIE materials and have potential application in various areas. In this review, we summarised the recent development of pillararene-based AIE materials from the following aspects: pillararenes as novel AIEgens, the TPE functionalized pillararene-based AIE materials, the pillararene-based AIE materials constructed by supramolecular assembly, and the functionalized pseudo-pillararene-based AIE materials. It is hoped that this feature article will attract increasing attention and pave a new way for the development and application of pillar[n]arene-based AIE materials in more fields.

N-(2-Aminoethyl)-2-(hexylthio) Acetamide-Functionalized Pillar[5]arene for the Selective Detection of l-Trp through Guest-Adaptive Multisupramolecular Interactions.

Tryptophan (Trp) is very necessary for biosystems; therefore, high-efficient detection of Trp is an important subject. Hereof, based on our early research works on fluorescent sensors, we rationally designed and synthesized a fluorescent sensor (SNP5) based on N-(2-aminoethyl)-2-(hexylthio) acetamide-functionalized pillar[5]arene, which showed high selectivity and sensitive recognition for l-Trp (LOD = 2.19 × 10-8 M). Moreover, SNP5 exhibited aggregation-induced emission enhancement fluorescence. Within SNP5, the pillar[5]arene group could act as N-H···π- and C-H···π-interaction sites, as well as a H-bond-interaction site; meanwhile, the N-(2-aminoethyl)-2-(hexylthio) acetamide group also served as a multihydrogen-bonding site. As a result, SNP5 could selectively detect l-Trp through the synergy of the pillar[5]arene group and the N-(2-aminoethyl)-2-(hexylthio) acetamide group. Compared with previous work, the results of this work support the strategy that changing the functionalized group of the pillar[5]arene can adjust the selectivity of the pillar[5]arene-based sensor and achieve the detection of different amino acids. The detection mechanism was specifically researched through experiments and theoretical calculations including frontier orbitals, electrostatic potential, and the independent gradient model approach. Interestingly, these theoretical calculations not only supported the experimental results but also provided a visualized understanding of guest-adaptive multisupramolecular interactions between SNP5 and l-Trp.

Metal-Free White Light-Emitting Fluorescent Material Based on Simple Pillar[5]arene-tripodal Amide System and Theoretical Insights on Its Assembly and Fluorescent Properties.

The booming of host-guest assembly-based supramolecular chemistry provides abundant ways to construct functional systems and materials. Attracted by the important application prospect of white light emission and aggregation-induced emission (AIE) materials, herein, we report an efficient way for fabricating metal-free white light-emitting AIE materials through the supramolecular assembly of simple organic compounds: methoxyl pillar[5]arene (MP5) and tri-(pyridine-4-ylamido)benzene (TAP). By host-guest assembly, MP5 and TAP formed a supramolecular polymer (MP5-T); meanwhile, the MP5-T xerogel powder emitted white light at CIE coordinates (0.29 and 0.29). The supramolecular assembly and white light-emitting mechanisms were carefully investigated by experiments as well as quantum chemical calculations including density functional theory (DFT), reduced density gradient, electrostatic surface potential, independent gradient model, and frontier molecular orbital (highest-occupied molecular orbital-lowest-unoccupied molecular orbital) analyses. Interestingly, according to the experiments and calculations, the supramolecular assembly is critical in the white light-emitting phenomenon. Moreover, in this work, the quantum chemical calculations could not only support experimental phenomena but also provide deep understanding and visualized presentation of the assembly and emission mechanism. In addition, the obtained MP5-T solid powder could serve as a novel and easy means to make material for white light-emitting devices.

A rhodamine-based dual chemosensor for the naked-eye detection of Hg2+ and enhancement of the fluorescence emission for Fe3.

A novel fluorescent chemosensor based on trimesoyl chloride-rhodamine (TR) was successfully synthesized. Rising chromogenic and fluorogenic spectral enhancements could be observed in trimesoyl chloride-rhodamine (TR) probes when Hg2+ and Fe3+ were added, respectively. TR has shown selectivity for Hg2+ and Fe3+ with high sensitivity due to metal ion complexation induced photophysical "turn-on" signaling responses. The detection limit towards Hg2+ was 2.46 × 10-8 M as determined by the 3σ method. At the same time, fluorogenic spectral enhancements were observed in TR, which exhibits a superior sensitive and selective recognition towards Fe3+ with 4.11 × 10-8 M of the detection limit. The test strips were used for colorimetric and simple detection towards Hg2+, which might finally enable the advancement of the Hg2+ sensor in the field of on-site detection.

A fluorescent supramolecular gel and its application in the ultrasensitive detection of CN- by anion-π interactions.

Supramolecular gels have been widely reported on account of their unique superiority and application prospects. In this work, we constructed a novel supramolecular gel (HD-G) by using hydroxy-naphthaldehyde decorated with naphthalimide in DMSO solution, which exhibited excellent selectivity and ultrasensitive sensing properties toward CN- (the lowest detection limit is 1.82 × 10-10 M). The sensing mechanism of this supramolecular gel takes advantage of π-π stacking interactions and anion-π interactions, which is different from the other familiar methods.