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| Open AccessSqueezing formaldehyde into C60 fullerene
The interconversion of the two spin isomers of formaldehyd has been studied in the gas phase but has never been observed experimentally in the condensed phase. Here the authors report the encapsulation of formaldehyde inside C60 cages and observe spin-isomer conversion of the formaldehyde guest molecules in the cryogenic solid state.
- Vijyesh K. Vyas
- , George R. Bacanu
- & Richard J. Whitby
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Article
| Open AccessSmart touchless human–machine interaction based on crystalline porous cages
Smart sensors are important components in the development of touchless human-machine interaction systems. Here, the authors describe a smart 3D porous crystalline organic cage-based system that exhibits remarkable responsiveness to fingertip humidity, contributing to the advancement of touchless human-machine interaction technology.
- Jinrong Wang
- , Weibin Lin
- & Niveen M. Khashab
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Article
| Open AccessComplexation-driven assembly of imine-linked helical receptors showing adaptive folding and temperature-dependent guest selection
The development of synthetic receptors capable of selectively binding monosaccharides is highly challenging. Here, authors present the efficient synthesis of these receptors based on foldamers, achieved through complexation-induced equilibrium shifting.
- Geunmoo Song
- , Seungwon Lee
- & Kyu-Sung Jeong
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Article
| Open AccessCounteranion-mediated efficient iodine capture in a hexacationic imidazolium organic cage enabled by multiple non-covalent interactions
The development of efficient adsorbents to capture iodine originating from radioactive wastes is of importance. Here, the authors synthesize hexacationic imidazolium organic cages and study the crucial role of the counter anions for iodine capture and the iodine binding modes at the molecular level on the solid state.
- Jian Yang
- , Shao-Jun Hu
- & Qing-Fu Sun
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Article
| Open AccessDual hypoxia-responsive supramolecular complex for cancer target therapy
The natural product BE-43547A2 (BE) could potentially serve as a template of hypoxia target strategy for treating pancreatic cancer, but the unsatisfactory pharmacokinetics profile and severe toxicity impeded the application of BE or its derivatives. Here the authors report a supramolecular dual hypoxia-responsive BE-based complex for achieving efficient drug delivery within tumors.
- Jian-Shuang Guo
- , Juan-Juan Li
- & Yue Chen
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Article
| Open AccessNonporous amorphous superadsorbents for highly effective and selective adsorption of iodine in water
Porous or crystalline materials are generally employed as adsorbents for environmental remediation. Here the authors employ nonporous and amorphous covalent organic superphane cages for aqueous iodine adsorption achieving good selectivity, high adsorption capability and fast kinetics.
- Wei Zhou
- , Aimin Li
- & Qing He
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Article
| Open AccessThe sharp structural switch of covalent cages mediated by subtle variation of directing groups
Controlling the self-assembly on noncovalent components is possible by suppressing entropy loss with templates but this is challenging for covalent components. Here the authors employed directing groups to endow purely covalent molecular building blocks with different conformations which favor the formation of specific self-assembled products.
- Qiong Chen
- , Zhaoyong Li
- & Hao Li
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Article
| Open AccessPreferential molecular recognition of heterochiral guests within a cyclophane receptor
The design of synthetic supramolecular receptors capable of enantioselective molecular recognition is challenging. Here the authors report a perylene bisimide-based receptor that forms heterochiral host-guest complexes upon aromatic guests encapsulation; guest recognition can be modulated by peripheral substitution of the binding site.
- Manuel Weh
- , Kazutaka Shoyama
- & Frank Würthner
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Article
| Open AccessSymmetry-breaking host–guest assembly in a hydrogen-bonded supramolecular system
Self-assembly processes usually yield symmetric compounds. Here, the authors report the distortion of a symmetric hydrogen-bonded resorcin[4]arene cage upon encapsulation of an iridium complex.
- Shinnosuke Horiuchi
- , Takumi Yamaguchi
- & Keisuke Umakoshi
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Article
| Open AccessReal-time chirality transfer monitoring from statistically random to discrete homochiral nanotubes
Monitoring chirality transfer during self-assembly processes is challenging. Here, the authors study the assembly of chiral pillar[5]arene-based nanotubes; diastereomerically pure trimeric nanotubes are synthesized from a mixture of pillar[5]arene compounds.
- Shixin Fa
- , Tan-hao Shi
- & Tomoki Ogoshi
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Article
| Open AccessWater-stable porous Al24 Archimedean solids for removal of trace iodine
The removal of radioactive elements is important to human health and sustainable development. Here, the authors reveal the synthesis of water-stable Archimedean solids based on the earth-abundant element for the fast removal of trace iodine.
- Ya-Jie Liu
- , Yi-Fan Sun
- & Jian Zhang
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Article
| Open AccessControllable DNA hybridization by host–guest complexation-mediated ligand invasion
Direct dissociation of nucleic acid duplex structures without heating or specific binding proteins is challenging. Here the authors use the cucurbit[7]uril-based host–guest system to construct a ligand-invasion pathway for controllable DNA hybridisation.
- Lin Xiao
- , Liang-Liang Wang
- & Liang Xu
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Article
| Open AccessSelective separation of light rare-earth elements by supramolecular encapsulation and precipitation
The separation of the rare-earth elements is a significant scientific challenge. Here, the authors report the selective precipitation of the light rare-earths as supramolecular capsules from acidic, industrially relevant, mixed-metal solutions.
- Joseph G. O’Connell-Danes
- , Bryne T. Ngwenya
- & Jason B. Love
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Article
| Open AccessChiral self-sorting and guest recognition of porous aromatic cages
The synthesis of stable chiral porous organic cages and the study of their chiral self-sorting properties is challenging. Here, the authors report axially chiral porous aromatic cages with high stability and solvent-controlled chiral self-sorting.
- Dong-Xu Cui
- , Yun Geng
- & Zhong-Min Su
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Article
| Open AccessType II porous ionic liquid based on metal-organic cages that enables l-tryptophan identification
Porous liquids are potentially useful materials for the identification and separation of non-gaseous compounds. Herein, the authors report a type II porous ionic liquid with permanent porosity and high selectivity towards l-tryptophan (l-Trp) over other aromatic amino acids.
- Zhuxiu Zhang
- , Baolin Yang
- & Xu Qiao
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Article
| Open AccessModifying electron injection kinetics for selective photoreduction of nitroarenes into cyclic and asymmetric azo compounds
Modifying the reactivity of substrates by encapsulation is essential for microenvironment catalysts. Herein, the authors report an alternative strategy that modifies the entry behaviour of reactants and substrates to control the electron injection kinetics, thus affecting the selectivity of nitroarene photoreductions.
- Yang Yang
- , Xu Jing
- & Chunying Duan
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Article
| Open AccessA host–guest semibiological photosynthesis system coupling artificial and natural enzymes for solar alcohol splitting
Abiotic–biotic hybrid systems are promising to trap light for fuel and chemical transformation with high efficacy and selectivity. This study reports a coenzyme-mediated supramolecular host-guest semibiological system combining supramolecular catalyst and enzymes for solar alcohol splitting.
- Junkai Cai
- , Liang Zhao
- & Chunying Duan
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Article
| Open AccessA curved host and second guest cooperatively inhibit the dynamic motion of corannulene
The preparation of artificial host–guest systems that display dynamic adaptation during guest binding is challenging. Here the authors report a chiral self-assembled tetrahedral cage featuring curved walls that reconfigures stereochemically to fit fullerene guests, regulates corannulene inversion, and enables the determination of co-guest enantiomeric excess by NMR spectroscopy.
- Yang Yang
- , Tanya K. Ronson
- & Jonathan R. Nitschke
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Article
| Open AccessEfficient ethylene purification by a robust ethane-trapping porous organic cage
The removal of ethane from ethylene is of importance in the petrochemical industry, but similar physicochemical properties of these molecules makes separation a challenging task. Here, the authors demonstrate that a robust octahedral calix[4]resorcinarene-based porous organic cage can separate high-purity ethylene from ethane/ethylene mixtures.
- Kongzhao Su
- , Wenjing Wang
- & Daqiang Yuan
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Article
| Open AccessOvertemperature-protection intelligent molecular chiroptical photoswitches
Realizing overtemperature protection with a molecular device is challenging. Here, the authors demonstrate an overtemperature protection function by integrating thermo- and photoresponsive functions into a pillar[6]arene based pseudocatanene.
- Jiabin Yao
- , Wanhua Wu
- & Cheng Yang
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Article
| Open AccessBiomimetic caged platinum catalyst for hydrosilylation reaction with high site selectivity
Design of artificial catalysts to mimic enzyme activity and selectivity is a challenge in the catalysis field. Here, the authors design a platinum catalyst with a porous cage ligand which shows enzyme-like properties, such as high hydrosilylation activity and substrate size selectivity, while being recyclable.
- Ganghuo Pan
- , Chunhua Hu
- & Yuzhou Liu
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Article
| Open AccessXenon binding by a tight yet adaptive chiral soft capsule
Xenon binding carries potential for xenon separation and emerging applications in magnetic resonance imaging. Here, the authors report a rare example of a tight yet soft capsule, assembled from two chiral bisurea-bisthiourea macrocycle components, that can efficiently and adaptively bind xenon in both the solid state and solution.
- Shi-Xin Nie
- , Hao Guo
- & Qi-Qiang Wang
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Article
| Open AccessThree host peculiarities of a cycloalkane-based micelle toward large metal-complex guests
Typical micelles are molecular assemblies composed of amphiphiles bearing linear alkyl chains. Herein, the authors present an uncommon type of cycloalkane-based bent amphiphile and its micelle which encapsulates large metal- complexes with high uptake efficiency, selectivity, and emissivity in water.
- Mamiko Hanafusa
- , Yamato Tsuchida
- & Michito Yoshizawa
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Article
| Open AccessMolecular motor-functionalized porphyrin macrocycles
Molecular motors and switches change conformation under the influence of an external stimulus and can be incorporated into functional systems, allowing the construction of adaptive materials and switchable catalysts. Here, the authors present two molecular motor-functionalized porphyrin macrocycles for future photo-switchable catalysis.
- Pieter J. Gilissen
- , Paul B. White
- & Roeland J. M. Nolte
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| Open AccessAbsolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach
Vibrational circular dichroism (VCD) spectroscopy can be useful for determining the absolute configuration of chiral molecules, as long as the signal intensities are high enough. Here, the authors establish the absolute configurations of two large chiral porphyrin cages and, notably, discover that host-guest binding enhances their VCD intensities.
- Jiangkun Ouyang
- , Anne Swartjes
- & Roeland J. M. Nolte
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Article
| Open AccessIntercellular communication between artificial cells by allosteric amplification of a molecular signal
The principles of intercellular communication in multicellular organisms can be explored using artificial cells. Here, the authors report on giant vesicles which can recognize diffused chemical signals and amplify the signal by synthetic enzymatic cascades to allow signal propagation over long distances.
- Bastiaan C. Buddingh’
- , Janneke Elzinga
- & Jan C. M. van Hest
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Article
| Open AccessSelf-assembled conjoined-cages
Developing simple routes for construction of multi-compartmental cages is a compelling and challenging task. Here, the authors report modular construction of multi-3D-cavity cages featuring one, two or three units of a [Pd2L4] entity conjoined with a [Pd3L6] core.
- Sagarika Samantray
- , Shobhana Krishnaswamy
- & Dillip K. Chand
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Article
| Open AccessInterplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold
Supramolecular catalytic assemblies attract enormous interest due to their activity that rivals natural enzymes. Using ab initio molecular dynamics, the authors show that a gold catalyst in a Ga4L612- nanocage, while impeded by reorganization energy, is accelerated by hosting a catalytic water molecule.
- Valerie Vaissier Welborn
- , Wan-Lu Li
- & Teresa Head-Gordon
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Article
| Open AccessA metal–peptide capsule by multiple ring threading
Constructing molecular cages from entangled molecules is a complex task requiring precise topological control. Here, the authors thread together six metal-peptide rings into a giant cubic molecular capsule with a defined cavity and 24 crossover points.
- Tomohisa Sawada
- , Yuuki Inomata
- & Makoto Fujita
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Article
| Open AccessA [13]rotaxane assembled via a palladium molecular capsule
Mechanically interlocked molecules and molecular cages are two important themes in supramolecular chemistry. Here, the authors combine these concepts to construct a giant [13]rotaxane built around a palladium capsule, one of the most complex metallosupramolecular assemblies yet.
- Jesus Ferrando-Soria
- , Antonio Fernandez
- & Richard E. P. Winpenny
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Article
| Open AccessSupramolecular trap for catching polyamines in cells as an anti-tumor strategy
Polyamines are essential for cell growth and are frequently increased in concentration in cancer cells. Here, the authors use a macrocycle to generate a supramolecular trap, which depletes the polyamines in cells, induces apoptosis and reduces cancer cell growth in mice.
- Junyi Chen
- , Hanzhi Ni
- & Chunju Li
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Article
| Open AccessChemical mimicry of viral capsid self-assembly via corannulene-based pentatopic tectons
The icosahedron, as the polyhedron closest in symmetry to the sphere, is one of the most compelling Platonic solids for chemists to construct. Here, the authors assemble a supramolecular icosahedron from twelve pentatopic corannulene-based tectons, a strategy that was proposed over a decade ago but only now synthetically realized.
- Yu-Sheng Chen
- , Ephrath Solel
- & Yi-Tsu Chan
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Article
| Open AccessPolyaromatic nanocapsules as photoresponsive hosts in water
Photoresponsive molecular capsules that can be used in water are rare. Here, the authors construct polyaromatic nanocapsules via self-assembly from photoswitch-bearing amphiphilic molecules in water. Light induces a structural change in the amphiphiles, triggering the capsule to disassemble into monomers and release encapsulated guests.
- Lorenzo Catti
- , Natsuki Kishida
- & Michito Yoshizawa
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Article
| Open AccessTemperature-controlled repeatable scrambling and induced-sorting of building blocks between cubic assemblies
In this paper, the authors study the temperature-controlled dynamic behavior of a system of nanocubes self-assembled from two different building blocks. Non-intuitively, the disordered, equilibrium state (a mixture of heteroleptic cubes) and the ordered, out-of-equilibrium state (a mixture of homoleptic cubes) are cycled by heating and subsequent rapid cooling.
- Yi-Yang Zhan
- , Tatsuo Kojima
- & Shuichi Hiraoka
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Article
| Open AccessInterconvertible vanadium-seamed hexameric pyrogallol[4]arene nanocapsules
Adapting the cavity of a coordination capsule generally involves the addition or removal of subcomponents. Here, the authors report two vanadium-organic coordination nanocapsules with the same number of components but variable cavity sizes—an expanded ball and contracted octahedron—whose solvent-controlled interconversion is attributed to the versatile coordination geometry of the vanadium centers.
- Kongzhao Su
- , Mingyan Wu
- & Maochun Hong
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Article
| Open AccessInduced-fit expansion and contraction of a self-assembled nanocube finely responding to neutral and anionic guests
Induced-fit binding, common in biological systems, is still relatively rare in artificial hosts. Here, the authors assemble a molecular cube from six gear-shaped faces, whose interdigitated design allows the cube to expand and contract in response to the size, shape, and charge of a guest molecule.
- Yi-Yang Zhan
- , Tatsuo Kojima
- & Shuichi Hiraoka
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Article
| Open AccessCramming versus threading of long amphiphilic oligomers into a polyaromatic capsule
Molecular capsules typically bind only guests with volumes smaller than their cavities. Here, the authors find that a polyaromatic capsule accommodates linear amphiphilic oligomers in a length-dependent manner, whereas short chains are fully crammed into the cavity, long chains can be incorporated into the capsule in a threaded fashion.
- Masahiro Yamashina
- , Shunsuke Kusaba
- & Michito Yoshizawa
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Article
| Open AccessHigh-throughput discovery of organic cages and catenanes using computational screening fused with robotic synthesis
Supramolecular assemblies remain of great importance to a variety of fields, yet their targeted design and synthesis remains highly challenging. Here, Cooper and colleagues combine computational screening with high-throughput robotic synthesis and discover 33 new organic cage molecules that form cleanly in one-pot syntheses.
- R. L. Greenaway
- , V. Santolini
- & A. I. Cooper
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Article
| Open AccessIn situ redox reactions facilitate the assembly of a mixed-valence metal-organic nanocapsule
New approaches are required to access metal-organic assemblies with unusual structural properties. Here, the authors use an in situ redox reaction to obtain a mixed-valence, Mn(II)/Mn(III)-containing metal-organic nanocapsule with an odd number of metal ions.
- Asanka S. Rathnayake
- , Hector W. L. Fraser
- & Jerry L. Atwood
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Article
| Open AccessHollow organic capsules assemble into cellular semiconductors
Perylene diimide-bithiophene macrocycles are electroactive and shape-persistent hosts. Here, the authors describe their self-assembly into a cellular organic semiconducting film whose voids are electrically sensitive to different guests, and which can function as the active layer in a field-effect transistor device.
- Boyuan Zhang
- , Raúl Hernández Sánchez
- & Colin Nuckolls
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Article
| Open AccessControl over multiple molecular states with directional changes driven by molecular recognition
Multistate molecular systems usually rely on external energy inputs to switch between states. Here, the authors show that a bispyridyl calixpyrrole system directed by only weak noncovalent interactions and metal coordination can access six discrete structural states, with directional and sequential control.
- Takehiro Hirao
- , Dong Sub Kim
- & Jonathan L. Sessler
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Article
| Open AccessReversible chromism of spiropyran in the cavity of a flexible coordination cage
Under confinement, molecular switches lose the conformational freedom often needed to isomerize. Here, the authors show that a flexible coordination cage can adapt its shape to guide the photoisomerization of encapsulated spiropyrans, rendering them reversibly photochromic even within the confines of the cavity.
- Dipak Samanta
- , Daria Galaktionova
- & Rafal Klajn
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Article
| Open AccessSequence-regulated copolymerization based on periodic covalent positioning of monomers along one-dimensional nanochannels
Achieving sequence control in polymers is limited by the relative monomer reactivity and thus often statistically random copolymers are obtained. Here the authors show sequence control in radical polymerizations by immobilising the monomer on a porous coordination polymer and subsequent polymerization with a second free monomer.
- Shuto Mochizuki
- , Naoki Ogiwara
- & Takashi Uemura
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Article
| Open AccessExact mass analysis of sulfur clusters upon encapsulation by a polyaromatic capsular matrix
The structures of inorganic clusters are commonly characterized by mass spectrometry (MS), but neutral sulfur clusters heavily fragment under MS conditions, preventing their exact mass determination. Here, the authors successfully perform MS on labile cyclic sulfur clusters by stabilizing them within ionic supramolecular capsules.
- Sho Matsuno
- , Masahiro Yamashina
- & Michito Yoshizawa
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Article
| Open AccessHigher-order assembly of crystalline cylindrical micelles into membrane-extendable colloidosomes
Functional nanoscale objects can be prepared via crystallization-driven self-assembly of diblock copolymers. Here the authors show the self-assembly of crystalline block copolymers into size-specific cylindrical micelles for the hierarchical construction of mechanically robust colloidosomes with a range of membrane textures.
- Hongjing Dou
- , Mei Li
- & Ian Manners
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Article
| Open AccessAnion-capped metallohost allows extremely slow guest uptake and on-demand acceleration of guest exchange
Host—guest assemblies can exploit stimuli-responsive guest binding and release for molecular recognition, but are typically governed by thermodynamics alone. Here, the authors design macrocycles with removable and exchangeable anion caps, allowing for the kinetic trapping and on-demand exchange of guest ions.
- Yoko Sakata
- , Chiho Murata
- & Shigehisa Akine
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Article
| Open AccessPolyaromatic molecular peanuts
The complex, multicomponent structures often found in nature are difficult to mimic synthetically. Here, the authors assemble a molecular analogue of a peanut through coordinative and π-stacking interactions, in which a polyaromatic double capsule ‘pod’ held together by metal ions encapsulates fullerene ‘beans’.
- Kohei Yazaki
- , Munetaka Akita
- & Michito Yoshizawa
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Article
| Open AccessAdaptive self-assembly and induced-fit transformations of anion-binding metal-organic macrocycles
Container-molecules capable of recognizing charged species possess great potential as sensors, but are typically limited by their rigid frameworks. Here, Sun and co-workers design a family of adaptive metal-organic macrocycles that exhibit shape and size induced-fit transformations upon anion-binding.
- Ting Zhang
- , Li-Peng Zhou
- & Qing-Fu Sun
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Article
| Open AccessUltra-large supramolecular coordination cages composed of endohedral Archimedean and Platonic bodies
Host–guest chemistry in hollow coordination cages can be exploited for a range of applications, but is often limited by inner cavity dimensions. Here, Schmitt and co-workers fabricate supramolecular keplerates that possess ultra-large cross-sectional diameters and are composed of multiple sub-cages.
- Kevin Byrne
- , Muhammad Zubair
- & Wolfgang Schmitt