Elongated‐Geminiarene: Syntheses, Solid‐State Conformational Investigations, and Application in Aromatics/Cyclic Aliphatics Separation

Wu, Jia‐Rui; Wang, Yan; Yang, Ying‐Wei

doi:10.1002/smll.202003490

Cited by 19 publications

(18 citation statements)

References 60 publications

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“…Moreover, the slight structural differences between the complexed guests, such as 1,3-dioxane and 1,4-dioxane, could induce a conformational interconversion between the two conformations, indicating an underlying solvent stimuli-responsive character of 13 in the solid state. Similar to 13 , two guest-loaded molecular conformations ( 15 α and 15 β) were also discovered in the binding systems of elongated-geminiarene 15 , where one exhibits a rigid stretched hexagon structure ( C i symmetry) and the other renders an unusual twisted molecular conformation ( C i symmetry) (Figure c,d).…”

Section: Structural Features and Host–guest Properties In The Solid S...mentioning

confidence: 76%

Pillararene-Inspired Macrocycles: From Extended Pillar[n]arenes to Geminiarenes

Yang

2022

Acc. Chem. Res.

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Conspectus Macrocyclic compounds have been the primary tools in supramolecular chemistry since their establishment due to their innate functional features of molecular recognition and complexation. The rapid development of modern supramolecular chemistry has also significantly benefited from creating new macrocycles with distinctive geometries and properties. For instance, pillar[n]arenes (pillarenes), a relatively young generation of star macrocyclic hosts among the well-established ones (e.g., crown ethers, cyclodextrins, cucurbiturils, and calixarenes), promoted a phenomenal research hotspot all over the world in the past decade. Although the synthesis, host–guest properties, and various supramolecular functions of pillarenes have been intensively studied, many objective limitations and challenges still cannot be ignored. For example, high-level pillar[n]arenes (n > 7) usually do not possess applicable large-sized cavities due to structural folding and cannot be synthesized on a large scale because of the uncompetitive cyclization process. Furthermore, two functional groups must be covalently para-connected to each repeating phenylene unit, which severely limits their structural diversity and flexibility. In this context, we have developed a series of pillarene-inspired macrocycles (PIMs) using a versatile and modular synthetic strategy during the past few years, aiming to break through the synthetic limitations in traditional pillarenes and find new opportunities and challenges in supramolecular chemistry and beyond. Specifically, by grafting biphenyl units into the pillarene backbones, extended pillar[n]arenes with rigid and nanometer-sized cavities could be obtained with reasonable synthetic yields by selectively removing hydroxy/alkoxy substitutes on pillarene backbones, leaning pillar[6]arenes and leggero pillar[n]arenes with enhanced structural flexibility and cavity adaptability were obtained. By combining the two types of bridging modes in pillarenes and calixarenes, a smart macrocyclic receptor with two different but interconvertible conformational features, namely geminiarene, was discovered. Benefiting from the synthetic accessibility, facile functionalization, and superior host–guest properties in solution or the solid state, this new family of macrocycles has exhibited a broad range of applications, including but not limited to supramolecular assembly/gelation/polymers, pollutant detection and separation, porous organic polymers, crystalline/amorphous molecular materials, hybrid materials, and controlled drug delivery. Thus, in this Account, we summarize our research efforts on these PIMs. We first present an overview of their design and modular synthesis and a summary of their derivatization strategies. Thereafter, particular attention is paid to their structural features, supramolecular functions, and application exploration. Finally, the remaining challenges and perspectives are outlined for their future development. We hope that this Account and our works can stimulate further advance...

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Section: Structural Features and Host–guest Properties In The Solid S...mentioning

confidence: 76%

Pillararene-Inspired Macrocycles: From Extended Pillar[n]arenes to Geminiarenes

Yang

2022

Acc. Chem. Res.

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“…Considering that tessellation of such category of macrocyclic polygons into highly ordered large-scale 2D tiling patterns required additional driving forces, outside binding was proposed as a novel strategy here. − In pillararene chemistry, outside binding was an almost unexplored area compared with the abundant in-cavity binding modes. − Benefiting from the electron-rich 1,4-dialkoxybenzene repeating units of pillar[ n ]arenes, the inspiration for the supramolecular tessellation was to introduce the charge-transfer (CT) interactions between donors (electron-rich pillar[ n ]arenes) and acceptors (electron-deficient guests) in the building blocks. , Propagation of the generated interactions in the CT assemblies was believed to direct the supramolecular tessellations with highly ordered tiling structure and morphology at the molecular level. Here, the electrostatic potential maps of TFB , DFN , and EtP6 were calculated to illustrate the possibility of the external complexation behaviors. − As shown in Figure b, the aromatic area of DFN and TFB displayed strong electropositivity.…”

Section: Results and Discussionmentioning

confidence: 99%

Supramolecular Tessellations via Pillar[n]arenes-Based Exo–Wall Interactions

Hua

Liang

et al. 2020

J. Am. Chem. Soc.

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Supramolecular tessellation is a newly emerging and promising area in supramolecular chemistry because of its unique structural aesthetics and potential applications. Herein, we investigate the "exo−wall" interactions of pillar[n]arenes and prepare fantastic hexagonal supramolecular tessellations based on perethylated pillar[6]arenes (EtP6) with electron-deficient molecules 1,5-difluoro-2,4-dinitrobenzene (DFN) and tetrafluoro-1,4benzoquinone (TFB). The crystal structures clearly confirm that EtP6 can form highly ordered hexagonal 2D tiling patterns with DFN/TFB as linkers through cocrystallization. Moreover, the selfassembled packing arrangements in the ultimate cocrystal superstructures can be adjusted under different crystallization conditions. This work not only explores the rare exo−wall interactions based on pillar[n]arenes but also reports the fabrication of supramolecular tessellations based on pillararenes for the first time, showing a new perspective in supramolecular chemistry.

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“…While the properties and applications of the robust pillararenes-based NACs are well-established, [2b,c, 18] new NACs based on pillararene derivatives and other important synthetic macrocycles,s uch as biphen [3]arene, [24] leaning pillar [6]arene (i.e., leaning tower [6]arene), [25] geminiarene, [26] bowtiearene, [27] cucurbit [6]uril, [23] hybrid [3]arene, [28] and tiara [5]arene [21] have been developed and recently reported. In this Minireview,w ed escribe some important progress in the development of synthetic macrocycles-based NACs, especially the constructions of NACs from newly discovered macrocyclic arenes for molecular separation and vapochromic application in the last two years.…”

Section: Reversible Transitions Betweenmentioning

confidence: 99%

Synthetic Macrocycle‐Based Nonporous Adaptive Crystals for Molecular Separation

Yang

2020

Angewandte Chemie

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The exploitation of new materials for adsorptive separation of industrially important hydrocarbons is of great importance in both scientific research and petrochemical industry. Nonporous adaptive crystals (NACs) as a robust class of synthetic materials have drawn much attention during the past five years for their superior performance in adsorption and separation. Pillararenes are the main family of macrocyclic arenes used for NACs construction, where the structure–function relationship has been intensively studied. In the past two years, some emerging types of synthetic macrocyclic arenes have been successfully brought into this research field, showing the gradual enrichment and diversification of NACs materials. This Minireview summarizes the recent advances of synthetic macrocycle‐based NACs, which are categorized by various practical applications in molecular separation. Besides, NACs‐based vapochromic supramolecular systems are also discussed. Finally, future perspectives and challenges of NACs are given. We envisage that this Minireview will be a useful and timely reference for those who are interested in new molecular and supramolecular crystals for storage and separation applications.

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Elongated‐Geminiarene: Syntheses, Solid‐State Conformational Investigations, and Application in Aromatics/Cyclic Aliphatics Separation

Cited by 19 publications

References 60 publications

Pillararene-Inspired Macrocycles: From Extended Pillar[n]arenes to Geminiarenes

Pillararene-Inspired Macrocycles: From Extended Pillar[n]arenes to Geminiarenes

Supramolecular Tessellations via Pillar[n]arenes-Based Exo–Wall Interactions

Synthetic Macrocycle‐Based Nonporous Adaptive Crystals for Molecular Separation

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