Abstract
Macrocyclic molecules have been used in various fields owing to their guest binding properties. Macrocycle-based host–guest chemistry in solution can allow for precise control of complex formation. Although solution-phase host–guest complexes are easily prepared, their limited stability and processability prevent widespread application. Extending host–guest chemistry from solution to the solid state results in complexes that are generally more robust, enabling easier processing and broadened applications. Macrocyclic compounds in the solid state can encapsulate guests with larger affinities than their soluble counterparts. This is crucial for use in applications such as separation science and devices. In this Review, we summarize recent progress in macrocycle-based solid-state host–guest chemistry and discuss the basic physical chemistry of these complexes. Representative macrocycles and their solid-state complexes are explored, as well as potential applications. Finally, perspectives and challenges are discussed.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Lehn, J.-M. Supramolecular chemistry — scope and perspectives molecules, supermolecules, and molecular devices (Nobel Lecture). Angew. Chem. Int. Ed. Engl. 27, 89–112 (1988).
Kolesnichenko, I. V. & Anslyn, E. V. Practical applications of supramolecular chemistry. Chem. Soc. Rev. 46, 2385–2390 (2017). This review presents the practical application studies of supramolecular chemistry from various aspects.
Liu, Z., Nalluri, S. K. M. & Stoddart, J. F. Surveying macrocyclic chemistry: from flexible crown ethers to rigid cyclophanes. Chem. Soc. Rev. 46, 2459–2478 (2017).
Xue, M., Yang, Y., Chi, X., Zhang, Z. & Huang, F. Pillararenes, a new class of macrocycles for supramolecular chemistry. Acc. Chem. Res. 45, 1294–1308 (2012).
Lee, J. W., Samal, S., Selvapalam, N., Kim, H.-J. & Kim, K. Cucurbituril homologues and derivatives: new opportunities in supramolecular chemistry. Acc. Chem. Res. 36, 621–630 (2003).
Zhao, D. & Moore, J. S. Shape-persistent arylene ethynylene macrocycles: syntheses and supramolecular chemistry. Chem. Commun. https://doi.org/10.1039/B207442G (2003).
Jana, A. et al. Functionalised tetrathiafulvalene- (TTF-) macrocycles: recent trends in applied supramolecular chemistry. Chem. Soc. Rev. 47, 5614–5645 (2018).
Guo, D.-S. & Liu, Y. Supramolecular chemistry of p-sulfonatocalix[n]arenes and its biological applications. Acc. Chem. Res. 47, 1925–1934 (2014).
Hua, Y. & Flood, A. H. Click chemistry generates privileged CH hydrogen-bonding triazoles: the latest addition to anion supramolecular chemistry. Chem. Soc. Rev. 39, 1262–1271 (2010).
Evans, N. H. & Beer, P. D. Advances in anion supramolecular chemistry: from recognition to chemical applications. Angew. Chem. Int. Ed. Engl. 53, 11716–11754 (2014).
Lehn, J.-M. Cryptates: the chemistry of macropolycyclic inclusion complexes. Acc. Chem. Res. 11, 49–57 (1978).
Li, J., Yim, D., Jang, W.-D. & Yoon, J. Recent progress in the design and applications of fluorescence probes containing crown ethers. Chem. Soc. Rev. 46, 2437–2458 (2017).
Murray, J., Kim, K., Ogoshi, T., Yao, W. & Gibb, B. C. The aqueous supramolecular chemistry of cucurbit[n]urils, pillar[n]arenes and deep-cavity cavitands. Chem. Soc. Rev. 46, 2479–2496 (2017). This is one of the most comprehensive review papers to describe macrocycle host–guest chemistry in the aqueous state.
He, Q., Vargas-Zúñiga, G. I., Kim, S. H., Kim, S. K. & Sessler, J. L. Macrocycles as ion pair receptors. Chem. Rev. 119, 9753–9835 (2019).
Liu, W., Samanta, S. K., Smith, B. D. & Isaacs, L. Synthetic mimics of biotin/(strept)avidin. Chem. Soc. Rev. 46, 2391–2403 (2017).
Yang, L.-P., Wang, X., Yao, H. & Jiang, W. Naphthotubes: macrocyclic hosts with a biomimetic cavity feature. Acc. Chem. Res. 53, 198–208 (2019).
Ni, X.-L. et al. Self-assemblies based on the ‘outer-surface interactions’ of cucurbit[n]urils: new opportunities for supramolecular architectures and materials. Acc. Chem. Res. 47, 1386–1395 (2014).
Zhu, H., Li, Q., Zhu, W. & Huang, F. Pillararenes as versatile building blocks for fluorescent materials. Acc. Mater. Res. 3, 658–668 (2022). This review reveals and summarizes the applications of pillararenes in studies of fluorescent materials.
Dsouza, R. N., Pischel, U. & Nau, W. M. Fluorescent dyes and their supramolecular host/guest complexes with macrocycles in aqueous solution. Chem. Rev. 111, 7941–7980 (2011).
Della Sala, P. et al. Prismarenes: a new class of macrocyclic hosts obtained by templation in a thermodynamically controlled synthesis. J. Am. Chem. Soc. 142, 1752–1756 (2020).
Li, Z., Song, N. & Yang, Y.-W. Stimuli-responsive drug-delivery systems based on supramolecular nanovalves. Matter 1, 345–368 (2019).
Yang, L., Tan, X., Wang, Z. & Zhang, X. Supramolecular polymers: historical development, preparation, characterization, and functions. Chem. Rev. 115, 7196–7239 (2015).
Atwood, J. L., Barbour, L. J., Jerga, A. & Schottel, B. L. Guest transport in a nonporous organic solid via dynamic van der Waals cooperativity. Science 298, 1000–1002 (2002).
Enright, G. D., Udachin, K. A., Moudrakovski, I. L. & Ripmeester, J. A. Thermally programmable gas storage and release in single crystals of an organic van der Waals host. J. Am. Chem. Soc. 125, 9896–9897 (2003).
Rissanen, K. Crystallography of encapsulated molecules. Chem. Soc. Rev. 46, 2638–2648 (2017).
Wang, D.-X. & Wang, M.-X. Exploring anion−π interactions and their applications in supramolecular chemistry. Acc. Chem. Res. 53, 1364–1380 (2020). This is a comprehensive review on the topic of anion−π interactions to reveal their theoretical studies and applications.
Schalley, C. A. Analytical Methods in Supramolecular Chemistry Vol. 1 (John Wiley & Sons, 2012).
Rissanen, K., Barbour, L. J. & MacGillivray, L. R. Structural macrocyclic supramolecular chemistry. CrystEngComm 16, 3644–3645 (2014).
Venkataraman, D., Lee, S., Zhang, J. & Moore, J. S. An organic solid with wide channels based on hydrogen bonding between macrocycles. Nature 371, 591–593 (1994).
White, N. G., Caballero, A. & Beer, P. D. Observation of strong halogen bonds in the solid state structures of bis-haloimidazolium macrocycles. CrystEngComm 16, 3722–3729 (2014).
Zhou, Y., Jie, K., Zhao, R. & Huang, F. Supramolecular‐macrocycle‐based crystalline organic materials. Adv. Mater. 32, 1904824 (2020).
Wu, J. R. & Yang, Y.-W. Synthetic macrocycle‐based nonporous adaptive crystals for molecular separation. Angew. Chem. Int. Ed. Engl. 60, 1690–1701 (2021).
Ji, X. et al. Adhesive supramolecular polymeric materials constructed from macrocycle-based host–guest interactions. Chem. Soc. Rev. 48, 2682–2697 (2019).
Xia, D. et al. Functional supramolecular polymeric networks: the marriage of covalent polymers and macrocycle-based host–guest interactions. Chem. Rev. 120, 6070–6123 (2020).
Zhao, Q. & Liu, Y. Tunable photo-luminescence behaviors of macrocycle-containing polymer networks in the solid-state. Chem. Commun. 54, 6068–6071 (2018).
Li, X., Li, Z. & Yang, Y.-W. Tetraphenylethylene‐interweaving conjugated macrocycle polymer materials as two‐photon fluorescence sensors for metal ions and organic molecules. Adv. Mater. 30, 1800177 (2018).
Chen, W. et al. Macrocycle-derived hierarchical porous organic polymers: synthesis and applications. Chem. Soc. Rev. 50, 11684–11714 (2021).
Mali, K. S., Pearce, N., De Feyter, S. & Champness, N. R. Frontiers of supramolecular chemistry at solid surfaces. Chem. Soc. Rev. 46, 2520–2542 (2017).
Lou, X. Y. & Yang, Y.-W. Pillar[n]arene‐based supramolecular switches in solution and on surfaces. Adv. Mater. 32, 2003263 (2020).
Shetty, A. S., Fischer, P. R., Stork, K. F., Bohn, P. W. & Moore, J. S. Assembly of amphiphilic phenylacetylene macrocycles at the air−water interface and on solid surfaces. J. Am. Chem. Soc. 118, 9409–9414 (1996).
Mohan, M. et al. Surface modification induced enhanced CO2 sorption in cucurbit[6]uril, an organic porous material. Phys. Chem. Chem. Phys. 19, 25564–25573 (2017).
Kayaci, F., Aytac, Z. & Uyar, T. Surface modification of electrospun polyester nanofibers with cyclodextrin polymer for the removal of phenanthrene from aqueous solution. J. Hazard. Mater. 261, 286–294 (2013).
Xue, J. Y. et al. Aromatic hydrocarbon macrocycles for highly efficient organic light-emitting devices with single-layer architectures. Chem. Sci. 7, 896–904 (2016).
Ikemoto, K. et al. Modular synthesis of aromatic hydrocarbon macrocycles for simplified, single-layer organic light-emitting devices. J. Org. Chem. 81, 662–666 (2016).
Cui, J. et al. Supermolecule cucurbituril subnanoporous carbon supercapacitor (SCSCS). Nano Lett. 21, 2156–2164 (2021).
Zhang, Y. et al. Three‐dimensional anionic cyclodextrin‐based covalent organic frameworks. Angew. Chem. Int. Ed. Engl. 56, 16313–16317 (2017).
Yang, W. et al. Microporous diaminotriazine-decorated porphyrin-based hydrogen-bonded organic framework: permanent porosity and proton conduction. Cryst. Growth Des. 16, 5831–5835 (2016).
Li, B. et al. An adaptive supramolecular organic framework for highly efficient separation of uranium via an in situ induced fit mechanism. J. Mater. Chem. A 3, 23788–23798 (2015).
Strutt, N. L. et al. Incorporation of an A1/A2-difunctionalized pillar[5]arene into a metal–organic framework. J. Am. Chem. Soc. 134, 17436–17439 (2012).
Smaldone, R. A. et al. Metal–organic frameworks from edible natural products. Angew. Chem. Int. Ed. Engl. 49, 8630–8634 (2010).
Thallapally, P. K. et al. Gas-induced transformation and expansion of a non-porous organic solid. Nat. Mater. 7, 146–150 (2008).
Tashiro, S. & Shionoya, M. Novel porous crystals with macrocycle-based well-defined molecular recognition sites. Acc. Chem. Res. 53, 632–643 (2020).
Pedrini, A. et al. Calixarene-based porous 3D polymers and copolymers with high capacity and binding energy for CO2, CH4 and Xe capture. J. Mater. Chem. A 9, 27353–27360 (2021).
Yang, Y.-D. et al. Time-dependent solid-state molecular motion and colour tuning of host–guest systems by organic solvents. Nat. Commun. 11, 77 (2020).
Zhao, W. et al. Linear supramolecular polymers driven by anion–anion dimerization of difunctional phosphonate monomers inside cyanostar macrocycles. J. Am. Chem. Soc. 141, 4980–4989 (2019).
Ogoshi, T. et al. Host–guest complexation of perethylated pillar[5]arene with alkanes in the crystal state. Angew. Chem. Int. Ed. Engl. 54, 9849–9852 (2015).
Wang, G. et al. Engineering a pillar[5]arene-based supramolecular organic framework by a co-crystallization method. Dalton Trans. 47, 5144–5148 (2018).
Tao, W. et al. Macrocycle-based supramolecular assembly: an alternative strategy for visualizing the mechanism of piezochromic luminescence. Dye. Pigment. 210, 110967 (2023).
Johnston, H. M., Palacios, P. M., Pierce, B. S. & Green, K. N. Spectroscopic and solid-state evaluations of tetra-aza macrocyclic cobalt complexes with parallels to the classic cobalt (II) chloride equilibrium. J. Coord. Chem. 69, 1979–1989 (2016).
Finke, A. D., Gross, D. E., Han, A. & Moore, J. S. Engineering solid-state morphologies in carbazole–ethynylene macrocycles. J. Am. Chem. Soc. 133, 14063–14070 (2011).
Hughes, A. R. & Blanc, F. Recent advances in probing host–guest interactions with solid state nuclear magnetic resonance. CrystEngComm 23, 2491–2503 (2021). This review provides a comprehensive summary of the applications of solid-state NMR spectroscopy in the field of host–guest interactions and presents unique insights into structural information and dynamics of guest molecules adsorbed in solid materials.
Hughes, A. R., Liu, M., Paul, S., Cooper, A. I. & Blanc, F. Dynamics in flexible pillar[n]arenes probed by solid-state NMR. J. Phys. Chem. C 125, 13370–13381 (2021).
Yuan, C. et al. Crystalline C–C and C = C bond-linked chiral covalent organic frameworks. J. Am. Chem. Soc. 143, 369–381 (2020).
Schaub, T. A. et al. Exploration of the solid-state sorption properties of shape-persistent macrocyclic nanocarbons as bulk materials and small aggregates. J. Am. Chem. Soc. 142, 8763–8775 (2020).
Ono, T. & Hisaeda, Y. Vapochromism of organic crystals based on macrocyclic compounds and inclusion complexes. Symmetry 12, 1903 (2020).
Schulz, M. et al. A calixarene-based metal–organic framework for highly selective NO2 detection. Angew. Chem. Int. Ed. Engl. 57, 12961–12965 (2018).
Royakkers, J. & Bronstein, H. Macrocyclic encapsulated conjugated polymers. Macromolecules 54, 1083–1094 (2021).
Yang, W. et al. Tiara[5]arenes: synthesis, solid-state conformational studies, host–guest properties, and application as nonporous adaptive crystals. Angew. Chem. Int. Ed. Engl. 59, 3994–3999 (2020).
Skorjanc, T., Shetty, D. & Trabolsi, A. Pollutant removal with organic macrocycle-based covalent organic polymers and frameworks. Chem 7, 882–918 (2021).
Jie, K. et al. Mechanochemical synthesis of pillar[5]quinone derived multi-microporous organic polymers for radioactive organic iodide capture and storage. Nat. Commun. 11, 1086 (2020).
Xu, W. L. et al. Single crystal to single crystal polymerization of a self-assembled diacetylene macrocycle affords columnar polydiacetylenes. Cryst. Growth Des. 14, 993–1002 (2014).
Alsbaiee, A. et al. Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer. Nature 529, 190–194 (2016).
Wang, Y. et al. Efficient separation of cis‐ and trans‐1,2‐dichloroethene isomers by adaptive biphen[3]arene crystals. Angew. Chem. Int. Ed. Engl. 58, 10281–10284 (2019).
Li, B., Cui, L. & Li, C. Macrocycle co-crystals showing vapochromism to haloalkanes. Angew. Chem. Int. Ed. Engl. 59, 22012–22016 (2020).
Sun, X. et al. Macrocycle-based crystalline sponge that stabilizes and lights up cationic aggregation-caused quenching dyes. Adv. Opt. Mater. 9, 2101670 (2021).
Li, S. et al. Synthesis and macrocyclization-induced emission enhancement of benzothiadiazole-based macrocycle. Nat. Commun. 13, 2850 (2022).
Marafie, J. A., Bradley, D. D. & Williams, C. K. Thermally stable zinc disalphen macrocycles showing solid-state and aggregation-induced enhanced emission. Inorg. Chem. 56, 5688–5695 (2017).
Benson, C. R. et al. Plug-and-play optical materials from fluorescent dyes and macrocycles. Chem 6, 1978–1997 (2020).
Ball, M. et al. Conjugated macrocycles in organic electronics. Acc. Chem. Res. 52, 1068–1078 (2019).
Mulay, S. V. et al. A macrocyclic oligofuran: synthesis, solid state structure and electronic properties. Chem. Sci. 10, 8527–8532 (2019).
Zhang, J. et al. The chiral interfaces fabricated by D/L-alanine-pillar[5]arenes for selectively adsorbing ctDNA. Chem. Commun. 55, 778–781 (2019).
Zhu, H. et al. Pillar[5]arene-based chiral 3D polymer network for heterogeneous asymmetric catalysis. Polym. Chem. 8, 7108–7112 (2017).
Zhang, Z. et al. Formation of linear supramolecular polymers that is driven by C−H⋅⋅⋅ π interactions in solution and in the solid state. Angew. Chem. Int. Ed. Engl. 50, 1397–1401 (2011).
Lan, S., Yang, X., Shi, K., Fan, R. & Ma, D. Pillarquinone‐based porous polymer for a highly‐efficient heterogeneous organometallic catalysis. ChemCatChem 11, 2864–2869 (2019).
Sun, Y. et al. A biomimetic chiral-driven ionic gate constructed by pillar[6]arene-based host–guest systems. Nat. Commun. 9, 2617 (2018).
Geng, W.-C., Sessler, J. L. & Guo, D.-S. Supramolecular prodrugs based on host–guest interactions. Chem. Soc. Rev. 49, 2303–2315 (2020). This is a comprehensive review on the topic of supramolecular prodrugs to reveal their theoretical host–guest interactions and applications.
Sayed, M. & Pal, H. An overview from simple host–guest systems to progressively complex supramolecular assemblies. Phys. Chem. Chem. Phys. 23, 26085–26107 (2021).
Yue, L., Yang, K., Lou, X.-Y., Yang, Y.-W. & Wang, R. Versatile roles of macrocycles in organic–inorganic hybrid materials for biomedical applications. Matter 3, 1557–1588 (2020).
Wu, G., Li, F., Tang, B. & Zhang, X. Molecular engineering of noncovalent dimerization. J. Am. Chem. Soc. 144, 14962–14975 (2022).
Liu, Z., Dai, X., Sun, Y. & Liu, Y. Organic supramolecular aggregates based on water‐soluble cyclodextrins and calixarenes. Aggregate 1, 31–44 (2020).
Cohen, Y. & Slovak, S. Diffusion NMR for the characterization, in solution, of supramolecular systems based on calixarenes, resorcinarenes, and other macrocyclic arenes. Org. Chem. Front. 6, 1705–1718 (2019). This report presents the common uses of diffusion NMR technology in the studies of host–guest interactions.
Song, N., Kakuta, T., Yamagishi, T. A., Yang, Y.-W. & Ogoshi, T. Molecular-scale porous materials based on pillar[n]arenes. Chem 4, 2029–2053 (2018).
Li, M. et al. Supramolecular tessellations via pillar[n]arenes-based exo-wall interactions. J. Am. Chem. Soc. 142, 20892–20901 (2020).
Han, X.-N., Han, Y. & Chen, C.-F. Supramolecular tessellations by the exo-wall interactions of pagoda[4]arene. Nat. Commun. 12, 6378 (2021).
Pedersen, C. J. Cyclic polyethers and their complexes with metal salts. J. Am. Chem. Soc. 89, 2495–2496 (1967).
Bradshaw, J. S. & Izatt, R. M. Crown ethers: the search for selective ion ligating agents. Acc. Chem. Res. 30, 338–345 (1997).
Ye, Q. et al. Cesium lead inorganic solar cell with efficiency beyond 18% via reduced charge recombination. Adv. Mater. 31, 1905143 (2019).
Warby, J. H. et al. Revealing factors influencing the operational stability of perovskite light-emitting diodes. ACS Nano 14, 8855–8865 (2020).
Zhu, C. et al. Supramolecular assembly of halide perovskite building blocks. J. Am. Chem. Soc. 144, 12450–12458 (2022).
Wei, P. et al. New wine in old bottles: prolonging room-temperature phosphorescence of crown ethers by supramolecular interactions. Angew. Chem. Int. Ed. Engl. 59, 9293–9298 (2020). The article reveals a novel supramolecular strategy to achieve RTP based on host–guest complexes of crown ethers and ions.
Zhu, W., Xing, H., Li, E., Zhu, H. & Huang, F. Room-temperature phosphorescence in the amorphous state enhanced by copolymerization and host–guest complexation. Macromolecules 55, 9802–9809 (2022).
Akutagawa, T. et al. Ferroelectricity and polarity control in solid-state flip-flop supramolecular rotators. Nat. Mater. 8, 342–347 (2009).
Song, X.-J. et al. Record enhancement of Curie temperature in host–guest inclusion ferroelectrics. J. Am. Chem. Soc. 143, 5091–5098 (2021).
Huang, C. R. et al. The first high‐temperature supramolecular radical ferroics. Angew. Chem. Int. Ed. Engl. 60, 16668–16673 (2021).
Wang, C., Zhang, T. & Lin, W. Rational synthesis of noncentrosymmetric metal–organic frameworks for second-order nonlinear optics. Chem. Rev. 112, 1084–1104 (2012).
Ye, X. et al. Two host–guest grown ether supramolecules show switchable phase transition, dielectric and second-harmonic generation effect. Dalton Trans. 51, 15074–15079 (2022).
Merzlyakova, E. et al. 18-Crown-6 coordinated metal halides with bright luminescence and nonlinear optical effects. J. Am. Chem. Soc. 143, 798–804 (2021).
Lin, R.-L., Liu, J.-X., Chen, K. & Redshaw, C. Supramolecular chemistry of substituted cucurbit[n]urils. Inorg. Chem. Front. 7, 3217–3246 (2020).
Liu, M. et al. Double‐cavity nor‐seco‐cucurbit[10]uril enables efficient and rapid separation of pyridine from mixtures of toluene, benzene, and pyridine. Angew. Chem. Int. Ed. Engl. 61, e202207209 (2022). This article provides an advanced example of highly efficient separation of benzene, toluene and pyridine through a solid-state double-cavity cucurbituril host.
Tian, J. et al. Cucurbit[7]uril: an amorphous molecular material for highly selective carbon dioxide uptake. Chem. Commun. 47, 7626–7628 (2011).
Liang, J. et al. Encapsulation of a porous organic cage into the pores of a metal–organic framework for enhanced CO2 separation. Angew. Chem. Int. Ed. Engl. 59, 6068–6073 (2020).
Liang, J. et al. A chemically stable cucurbit[6]uril-based hydrogen-bonded organic framework for potential SO2/CO2 separation. J. Mater. Chem. A 8, 19799–19804 (2020).
Pan, S. et al. Selectivity in gas adsorption by molecular cucurbit[6]uril. J. Phys. Chem. C 120, 13911–13921 (2016).
Liu, M. et al. Pyridine detection using supramolecular organic frameworks incorporating cucurbit[10]uril. ACS Appl. Mater. Interfaces 13, 7434–7442 (2021).
Li, Q., Jie, K. & Huang, F. Highly selective separation of minimum‐boiling azeotrope toluene/pyridine by nonporous adaptive crystals of cucurbit[6]uril. Angew. Chem. Int. Ed. Engl. 59, 5355–5358 (2020).
Jie, K., Zhou, Y., Li, E. & Huang, F. Nonporous adaptive crystals of pillararenes. Acc. Chem. Res. 51, 2064–2072 (2018). This is a comprehensive review on NACs of pillararenes, revealing their definition and applications.
Wu, Y. et al. Selective separation of methylfuran and dimethylfuran by nonporous adaptive crystals of pillararenes. J. Am. Chem. Soc. 142, 19722–19730 (2020).
Zhou, Y., Jie, K., Zhao, R., Li, E. & Huang, F. Highly selective removal of trace isomers by nonporous adaptive pillararene crystals for chlorobutane purification. J. Am. Chem. Soc. 142, 6957–6961 (2020).
Nie, H., Wei, Z., Ni, X.-L. & Liu, Y. Assembly and applications of macrocyclic-confinement-derived supramolecular organic luminescent emissions from cucurbiturils. Chem. Rev. 122, 9032–9077 (2022).
Zhang, Z.-Y., Chen, Y. & Liu, Y. Efficient room-temperature phosphorescence of a solid-state supramolecule enhanced by cucurbit[6]uril. Angew. Chem. Int. Ed. Engl. 58, 6028–6032 (2019).
Zhang, Z.-Y. & Liu, Y. Ultralong room-temperature phosphorescence of a solid-state supramolecule between phenylmethylpyridinium and cucurbit[6]uril. Chem. Sci. 10, 7773–7778 (2019).
Zhang, Z.-Y. et al. A synergistic enhancement strategy for realizing ultralong and efficient room-temperature phosphorescence. Angew. Chem. Int. Ed. Engl. 59, 18748–18754 (2020).
Liu, S., Zavalij, P. Y. & Isaacs, L. Cucurbit[10]uril. J. Am. Chem. Soc. 127, 16798–16799 (2005).
Geng, J.-S. et al. Controllable photomechanical bending of metal–organic rotaxane crystals facilitated by regioselective confined-space photodimerization. Nat. Commun. 13, 2030 (2022).
Wu, H. et al. High-efficiency gold recovery using cucurbit[6]uril. ACS Appl. Mater. Interfaces 12, 38768–38777 (2020).
Lin, R. L. et al. Selective recovery and detection of gold with cucurbit[n]urils (n = 5–7). Inorg. Chem. 59, 3850–3855 (2020).
Wu, H. et al. Selective separation of hexachloroplatinate(IV) dianions based on exo-binding with cucurbit[6]uril. Angew. Chem. Int. Ed. Engl. 60, 17587–17594 (2021).
Ogoshi, T., Yamagishi, T.-A. & Nakamoto, Y. Pillar-shaped macrocyclic hosts pillar[n]arenes: new key players for supramolecular chemistry. Chem. Rev. 116, 7937–8002 (2016).
Jie, K. et al. Styrene purification by guest-induced restructuring of pillar[6]arene. J. Am. Chem. Soc. 139, 2908–2911 (2017).
Cao, J. et al. Separation of pyrrolidine from tetrahydrofuran by using pillar[6]arene-based nonporous adaptive crystals. Chem. Sci. 13, 7536–7540 (2022).
Wang, Z. et al. Efficient purification of 2,6-lutidine by nonporous adaptive crystals of pillararenes. ACS Appl. Mater. Interfaces 14, 41072–41078 (2022).
Li, E., Zhu, W., Fang, S., Jie, K. & Huang, F. Reimplementing guest shape sorting of nonporous adaptive crystals via substituent-size-dependent solid–vapour postsynthetic modification. Angew. Chem. Int. Ed. Engl. 61, e202211780 (2022).
Li, B. et al. Capture of sulfur mustard by pillar[5]arene: from host–guest complexation to efficient adsorption using nonporous adaptive crystals. iScience 23, 101443 (2020).
Li, Q., Zhu, H. & Huang, F. Alkyl chain length-selective vapour-induced fluorochromism of pillar[5]arene-based nonporous adaptive crystals. J. Am. Chem. Soc. 141, 13290–13294 (2019).
Song, C.-L., Li, Z., Wu, J.-R., Lu, T. & Yang, Y.-W. Intramolecular through-space interactions induced emission of pillar[4]arene[1]dicyanobenzene. Chem. Mater. 34, 10181–10189 (2022).
Hua, B. et al. Supramolecular solid-state microlaser constructed from pillar[5]arene-based host–guest complex microcrystals. J. Am. Chem. Soc. 140, 15651–15654 (2018).
Hua, B. et al. Pillar[5]arene-based solid-state supramolecular polymers with suppressed aggregation-caused quenching effects and two-photon excited emission. J. Am. Chem. Soc. 142, 16557–16561 (2020).
Wu, J.-R. & Yang, Y.-W. New opportunities in synthetic macrocyclic arenes. Chem. Commun. 55, 1533–1543 (2019).
Mao, L. et al. Highly efficient synthesis of non-planar macrocycles possessing intriguing self-assembling behaviors and ethene/ethyne capture properties. Nat. Commun. 11, 5806 (2020).
Wu, J.-R. & Yang, Y.-W. Geminiarene: molecular scale dual selectivity for chlorobenzene and chlorocyclohexane fractionation. J. Am. Chem. Soc. 141, 12280–12287 (2019).
Luo, D., Tian, J., Sessler, J. L. & Chi, X. Nonporous adaptive calix[4]pyrrole crystals for polar compound separations. J. Am. Chem. Soc. 143, 18849–18853 (2021).
Yang, Y.-D., Chen, X.-L., Sessler, J. L. & Gong, H.-Y. Emergent self-assembly of a multicomponent capsule via iodine capture. J. Am. Chem. Soc. 143, 2315–2324 (2021).
Zhou, H.-Y., Zhang, D.-W., Li, M. & Chen, C.-F. A calix[3]acridan-based host–guest cocrystal exhibiting efficient thermally activated delayed fluorescence. Angew. Chem. Int. Ed. Engl. 61, e202117872 (2022).
Wang, Y. et al. Two-photon excited deep-red and near-infrared emissive organic co-crystals. Nat. Commun. 11, 4633 (2020).
Yu, C.-M., Meng, X., Liu, X., Zhang, Z.-Y. & Li, C. Switchable supramolecular jalousie constructed from a fluorenone macrocycle. Chem. Mater. 34, 358–365 (2022).
Acknowledgements
F.H. thanks the National Key Research and Development Program of China (2021YFA0910100), the National Natural Science Foundation of China (22035006), Zhejiang Provincial Natural Science Foundation of China (LD21B020001) and the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study (SN-ZJU-SIAS-006) for financial support. F.H. thanks the Chemistry Instrumentation Center of Zhejiang University for technical support.
Author information
Authors and Affiliations
Contributions
H.Z. and F.H. conceived the idea and drafted the proposal. H.Z. wrote most of the content. L.C. completed all graphic tasks. B.S. and H.L. wrote the solid versus solution section. M.W. wrote the crown ether section. H.Z., F.H., H.L. and J.F.S. edited and revised the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Reviews Chemistry thanks Harry Gibson, Jonathan Sessler, Ying-Wei Yang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Zhu, H., Chen, L., Sun, B. et al. Applications of macrocycle-based solid-state host–guest chemistry. Nat Rev Chem 7, 768–782 (2023). https://doi.org/10.1038/s41570-023-00531-9
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41570-023-00531-9