Recent advances in the synthesis and applications of macrocyclic arenes.

Macrocyclic arenes including calixarenes, resorcinarenes, cyclotriveratrylene, pillararenes and so on have emerged as highly attractive synthetic macrocyclic hosts due to their unique structures, facile functionalization, and broad range of applications. In recent years, there has been growing interest in the development of novel macrocyclic arenes composed of various aromatic building blocks bridged by methylene groups, which have found applications in various research areas. Consequently, the development of novel macrocyclic arenes has become a frontier and hot topic in supramolecular and macrocyclic chemistry. In this review, we feature the recent advances in the synthesis and applications of novel macrocyclic arenes that have emerged in the last decade. The general synthetic strategies employed for these macrocyclic arenes are systematically summarized, and their wide applications in molecular recognition and assemblies, molecular machines, biomedical science and functional materials are highlighted.

Macrocycle-Based Charge Transfer Cocrystals with Dynamically Reversible Chiral Self-Sorting Display Chain Length-Selective Vapochromism to Alkyl Ketones.

Chirality-driven self-sorting plays an essential role in controlling the biofunction of biosystems, such as the chiral double-helix structure of DNA from self-recognition by hydrogen bonding. However, achieving precise control over the chiral self-sorted structures and their functional properties for the bioinspired supramolecular systems still remains a challenge, not to mention realizing dynamically reversible regulation. Herein, we report an unprecedented saucer[4]arene-based charge transfer (CT) cocrystal system with dynamically reversible chiral self-sorting synergistically induced by chiral triangular macrocycle and organic vapors. It displays efficient chain length-selective vapochromism toward alkyl ketones due to precise modulation of optical properties by vapor-induced diverse structural transformations. Experimental and theoretical studies reveal that the unique vapochromic behavior is mainly attributed to the formation of homo- or heterochiral self-sorted assemblies with different alkyl ketone guests, which differ dramatically in solid-state superstructures and CT interactions, thus influencing their optical properties. This work highlights the essential role of chiral self-sorting in controlling the functional properties of synthetic supramolecular systems, and the rarely seen controllable chiral self-sorting at the solid-vapor interface deepens the understanding of efficient vapochromic sensors.

Naphth[4]arene: Synthesis, Conformations, and Application in Color-Tunable Supramolecular Crystalline Assemblies.

Although the chemistry of macrocyclic arenes has seen rapid development in recent years, the synthesis of new macrocyclic arenes from aromatic rings with no directing groups remains a challenge. In this work, a new macrocyclic arene, naphth[4]arene (NA[4]A), composed of four naphthalene rings bridged by methylene groups, was synthesized using macrocycle-to-macrocycle conversion. NA[4]A shows 1,3-alternate and 1,2-alternate conformations in the solid state, which can be selectively obtained. By supramolecular co-assembly of NA[4]A and 1,2,4,5-tetracyanobenzene (TCNB) in different concentrations and temperatures, two conformation-dependent crystalline luminescent co-assemblies 1,2-NTC and 1,3-NTC can be selectively prepared. Interestingly, the two charge-transfer crystalline assemblies containing NA[4]A with different conformations show bright yellow and green fluorescence, and also display high photoluminescence quantum yields (PLQYs) of 45 % and 43 %. Furthermore, they exhibit color-tunable two-photon excited upconversion emission.

Enantiomeric Water-Soluble Octopus[3]arenes for Highly Enantioselective Recognition of Chiral Ammonium Salts in Water.

Study of enantioselective recognition in water by synthetic chiral macrocyclic receptors is undoubtedly of theoretical and practical significance, but it is a big challenge to achieve the enantioselective recognition with both high enantioselectivity and high affinity in water probably due to the deficiency of such water-soluble macrocyclic receptors with stable chiral cavities. Herein, we report a new class of chiral macrocyclic arenes named octopus[3]arenes. The enantiomeric macrocycles are composed of three homochiral ethenoanthracene subunits, and they can be synthesized by two pathways and then easily converted into water-soluble octopus[3]arenes P-1 and M-1. Notably, P-1 and M-1 with the rigid hexagonal structures and stable chiral hydrophobic cavities exhibit highly enantioselective recognition towards three pairs of chiral ammonium salts in water with the association constant up to 106  M-1 and the S/R selectivity up to 12.89.

Pagoda[4]arene and i-Pagoda[4]arene.

A new type of macrocyclic arenes, named pagoda[4]arene (P4) and i-pagoda[4]arene (i-P4), were conveniently synthesized by the TFA-catalyzed one-pot condensation of 2,6-dimethoxylanthracene and paraformaldehyde in dichloromethane at room temperature. P4 and i-P4 showed unique square pagoda structures and fixed conformations in solution and also exhibited strong blue fluorescence. Moreover, P4 and i-P4 with deep and rich-electron cavities could not only encapsulate n-hexane and one or two dichloromethane molecules in the solid state but also showed strong binding abilities toward neutral dinitriles with different chain lengths and various nitrogen-containing heterocyclic salts to form 1:1 stable host-guest complexes in both solution and the solid state. In particular, it was also found that with the increase in the alkyl chain length of the dinitriles, the association constants for their complexes with both P4 and i-P4 were markedly increased from glutaronitrile to octanedinitrile as a result of the deep cavities of the macrocycles and multiple intermolecular interactions. Since P4 and i-P4 had stable planar chirality, their efficient resolutions were further achieved by HPLC with a chiral column. Interestingly, the two enantiomers showed mirror-imaged CD signals and excellent CPL properties, which could allow them to have potential applications in chiral luminescent materials.

Helic[1]triptycene[3]arene: Synthesis, Complexation, and Formation of [2]Rotaxane Shuttle.

A new macrocyclic arene, helic[1]triptycene[3]arene H, was conveniently synthesized in 37% yield by a one-pot reaction starting from 2,6-dimethoxyl-3,7-dihydroxymethyltriptycene. Macrocycle H showed fixed conformation in solution and could form 1:1 complexes with a series of neutral guests, secondary ammonium salts, and tertiary ammonium salts in both solution and solid states. The association constants between H and the neutral guests were between (1.23 ± 0.10) × 102 and (4.70 ± 0.47) × 103 M-1, while the association constants between H and the ammonium guests were between (1.35 ± 0.12) × 103 and (1.59 ± 0.14) × 105 M-1. Moreover, H showed bigger association constants with secondary ammonium salts than those with tertiary ammonium salts possibly because of the steric hindrance effect and multiple intermolecular interactions. The stimuli-responsive complexation between H and the ammonium salts could be controlled by the addition and removal of acids and bases as well. Based on the host-guest complexation between H and the secondary ammonium salt, [2]rotaxane was further synthesized, and its shuttling motion could be efficiently controlled by an acid and base.

Strategies for Constructing Macrocyclic Arene-Based Color-Tunable Supramolecular Luminescent Materials.

Over the past decades, supramolecular luminescent materials (SLMs) have attracted considerable attention due to their dynamic noncovalent interactions, versatile functions, and intriguing applications in many research fields. From construction to application, great efforts and progress have been made in color-tunable SLMs in recent years. In order to realize multicolor luminescence, various design strategies have been proposed. Macrocyclic chemistry, one of the brightest jewels in the field of supramolecular chemistry, has played a crucial role in the construction of stimuli-responsive and emission-tunable SLMs. Moreover, the flexible and tunable conformation and multiple noncovalent complexation sites of the macrocyclic arenes (MAs) afford a new opportunity to create such dynamic smart luminescent materials. Inspired by our reported work on the color-tunable supramolecular crystalline assemblies modulated by the conformation of naphth[4]arene, this Concept provides a summary of the latest developments in the construction of color-tunable MA-based SLMs, accompanied by the various construction strategies. The aim is to provide researchers with a new perspective to construct color-tunable SLMs with fascinating functions.

Octopus[5]arene from Pagoda[5]arene by Macrocycle-to-Macrocycle Conversion.

Macrocycle-to-macrocycle conversion is an effective strategy to construct new macrocyclic arenes with specific structures. Herein, a new class of chiral macrocyclic arene, namely, octopus[5]arenes (Oc5s), cannot be synthesized by the direct approach from the corresponding chiral monomers but can be successfully achieved by a macrocycle-to-macrocycle conversion strategy utilizing racemic pagoda[5]arenes as the starting materials. It was found that enantiomeric Oc5s showed fixed conformations and stable chiral structures and exhibited significant chiral recognition toward chiral diamines.

Advances in circularly polarized luminescence materials based on chiral macrocycles.

Development of circularly polarized luminescence (CPL) materials utilizing supramolecular strategies has recently attracted increasing interest in supramolecular chemistry and materials science. Chiral macrocycles, especially chiral macrocyclic hosts, have stable structures, adjustable internal cavities to encapsulate different guests, and host-guest complexation to induce special photophysical properties. Consequently, various CPL materials based on chiral macrocycles have been developed during the last decade. To gain a better understanding of this rapidly developing research area, it is necessary and also important to summarize the advances in CPL materials based on chiral macrocycles. In this review, CPL materials from different chiral macrocycles, especially classical and newly reported chiral macrocyclic hosts and their derivatives, will be comprehensively summarized. It is believed that this review will be of guiding significance and also very helpful for the development of macrocyclic chemistry and CPL materials.

Pagoda[n]arenes (n = 4, 5): Extremely Strong Binders for the Tropylium Cation.

Herein, host-guest complexation between pagoda[n]arenes (n = 4, P4; n = 5, P5) and tropylium cation (G) was investigated in detail. It was found that both P4 and P5 showed surprisingly strong binding affinities toward the tropylium cation with association constants of more than 107 M-1 for the 1:1 host-guest complexes. The theoretical calculations showed different host-guest complexion ways for complexes G@P4 and G@P5 and the strong π···π interactions and multiple C-H···π interactions play a very important role in the formation of these stable complexes, respectively. Moreover, the switchable processes of guest binding and release in the complexes can be effectively controlled by redox stimuli, and they can be also visible by the color and fluorescence changes.

Complexation with pagoda[n]arene (n = 4, 5) protects ferrocenium from oxidation.

The complexation behaviors of pagoda[n]arenes (n = 4, 5) with ferrocene, ferrocenium and analogues cobaltocenium were studied. The inclusion complexes of pagoda[n]arenes can protect ferrocenium from oxidation in organic solvents and improve the stability and oxygen resistance of ferrocenium.

Inherently chiral belt-shaped conjugated macrocycles with strong fluorescence and circularly polarized luminescence.

A pair of inherently chiral belt-shaped conjugated macrocycles were conveniently synthesized starting from 2,7-fluoren[3]arene triflate, and they not only exhibited green fluorescence, but also showed circularly polarized luminescence with a |glum| of 2.0 × 10-3.

A novel thermally activated delayed fluorescence macrocycle.

A novel luminescent macrocycle has been conveniently synthesized, which displays flexible conformations and interesting solid-state host-guest properties. Besides, the macrocycle exhibits excellent thermally activated delayed fluorescence (TADF) emission with a photoluminescence quantum yield of 80%, which represents the highest value among reported TADF macrocycles.

Supramolecular tessellations by the exo-wall interactions of pagoda[4]arene.

Supramolecular tessellation has gained increasing interest in supramolecular chemistry for its structural aesthetics and potential applications in optics, magnetics and catalysis. In this work, a new kind of supramolecular tessellations (STs) have been fabricated by the exo-wall interactions of pagoda[4]arene (P4). ST with rhombic tiling pattern was first constructed by P4 itself through favorable π···π interactions between anthracene units of adjacent P4. Notably, various highly ordered STs with different tiling patterns have been fabricated based on exo-wall charge transfer interactions between electron-rich P4 and electron-deficient guests including 1,4-dinitrobenzene, terephthalonitrile and tetrafluoroterephthalonitrile. Interestingly, solvent modulation and guest selection played a crucial role in controlling the molecular arrangements in the co-crystal superstructures. This work not only proves that P4 is an excellent macrocyclic building block for the fabrication of various STs, but also provides a new perspective and opportunity for the design and construction of supramolecular two-dimensional organic materials.

D-π*-A type planar chiral TADF materials for efficient circularly polarized electroluminescence.

Planar chiral organic fluorescent materials that exhibit high chiral stability, high efficiency and circularly polarized luminescence (CPL) currently remain an unresolved issue despite their promising applications in optical encryption and 3D-display. Herein, a pair of new donor-chiral π-acceptor (D-π*-A) type planar chiral thermally activated delayed fluorescence (TADF) enantiomers, namely R/S-PXZ-PT, are developed. Such a D-π*-A type structure completely suppresses the racemisation of the planar chirality, making it possible to prepare circularly polarized organic light-emitting diodes (CP-OLEDs) by vacuum deposition processing. Moreover, this design perfectly integrates the chiral unit into the luminescent unit to achieve intense CPL activity with luminescence asymmetry factors (glum) of ±1.9 × 10-3. Notably, the enantiomer-based devices exhibit a yellow coloured emission with a maximum external quantum efficiency (EQE) of 20.1%, and mirror-image circularly polarized electroluminescence signals with electroluminescence dissymmetry factors (gEL) of +1.5 × 10-3/-1.3 × 10-3. This work not only enriches the diversity of chiral TADF molecular design, but also provides a new perspective for the development of highly-efficient CP-OLEDs with stable planar chiral TADF materials.