Biphen[<i>n</i>]arenes: Modular Synthesis, Customizable Cavity Sizes, and Diverse Skeletons

Zhang, Zhiyuan; Li, Chunju

doi:10.1021/acs.accounts.2c00043

Cited by 99 publications

(60 citation statements)

References 70 publications

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“…While the synthetic method, host–guest chemistry, and diversified application exploration of the traditional pillarenes have been wildly investigated, new macrocyclic compounds inspired by pillarenes are being unearthed continuously and reported on today, − ,− aiming to break through some bottleneck scientific problems which cannot be well resolved or explained by traditional pillarenes. For example, high-level pillar[ n ]arenes ( n > 7) are usually obtained with extremely low synthetic yields and also do not have effective large-sized binding cavities because of structural folding .…”

Section: Introductionmentioning

confidence: 99%

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: Introductionmentioning

confidence: 99%

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

Yang

2022

Acc. Chem. Res.

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“…During the past few decades, a number of novel supramolecular macrocycles have emerged, such as crown ethers, [23][24][25][26][27][28][29] cyclodextrins, [30][31][32][33][34][35] calixarenes, [36][37][38] cucurbiturils, [39][40][41][42][43] pillararenes, [44][45][46][47][48][49][50] coronarenes, 51 cyclophanes 52 and others, [53][54][55][56][57] greatly enriching the toolkit of supramolecular chemists. Biphen[n]arenes, [58][59][60]68 including basic biphen[n]arenes, functional biphen[n]arenes, and cage compounds, are new macrocyclic hosts that appeared in the supramolecular world recently. Their repeating units 4,4 0 -biphenol or 4,4 0 -biphenol ether are linked by methylene bridges at the 3-and 3 0 -positions.…”

Section: Introductionmentioning

confidence: 99%

“…The unique geometries and easy chemical functionalization of biphenarenes endow them with remarkable abilities to selectively bind a variety of guests and make them promising candidates for fabricating a wide variety of interesting supramolecular materials. [61][62][63][64][65][66][67][68] Herein, we prepared a new amphiphilic water-soluble biphen [3]arene H using a facile method (Scheme 1). Compound EtBP3 was synthesized using a one-step procedure previously reported by Li's group.…”

Section: Introductionmentioning

confidence: 99%

An amphiphilic water-soluble biphen[3]arene with a tunable lower critical solution temperature behavior

et al. 2022

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“…16 Also Zhang and Li studied the customizable size of biphen[ n ]arenes and how it affects the host–guest interactions. 17 These pillararenes are supramolecular macrocycles containing cavities to capture a range of small molecules through host–guest properties. 18 The fascinating aspect of these molecules is that their π-rich cavities can encapsulate molecules selectively by non-covalent interactions.…”

Section: Introductionmentioning

confidence: 99%