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The complex distribution of functional groups in carbohydrates, coupled with their strong solvation in water, makes them challenging targets for synthetic receptors. Despite extensive research into various molecular frameworks, most synthetic carbohydrate receptors have exhibited low affinities, and their interactions with sugars in aqueous environments remain poorly understood. In this work, we present a simple pyridinium-based hydrogen-bonding receptor derived from a subtle structural modification of a well-known tetralactam macrocycle. This small structural change resulted in a dramatic enhancement of glucose binding affinity, increasing from 56 M−1 to 3001 M−1. Remarkably, the performance of our synthetic lectin surpasses that of the natural lectin, concanavalin A, by over fivefold. X-ray crystallography of the macrocycle–glucose complex reveals a distinctive hydrogen bonding pattern, which allows for a larger surface overlap between the receptor and glucose, contributing to the enhanced affinity. Furthermore, this receptor possesses allosteric binding sites, which involve chloride binding and trigger receptor aggregation. This unique allosteric process reveals the critical role of structural flexibility in this hydrogen-bonding receptor for the effective recognition of sugars. We also demonstrate the potential of this synthetic lectin as a highly sensitive glucose sensor in aqueous solutions. 

Abstract Developing an eco-friendly, efficient, and highly selective gold-recovery technology is urgently needed in order to maintain sustainable environments and improve the utilization of resources. Here we report an additive-induced gold recovery paradigm based on precisely controlling the reciprocal transformation and instantaneous assembly of the second-sphere coordinated adducts formed between β-cyclodextrin and tetrabromoaurate anions. The additives initiate a rapid assembly process by co-occupying the binding cavity of β-cyclodextrin along with the tetrabromoaurate anions, leading to the formation of supramolecular polymers that precipitate from aqueous solutions as cocrystals. The efficiency of gold recovery reaches 99.8% when dibutyl carbitol is deployed as the additive. This cocrystallization is highly selective for square-planar tetrabromoaurate anions. In a laboratory-scale gold-recovery protocol, over 94% of gold in electronic waste was recovered at gold concentrations as low as 9.3 ppm. This simple protocol constitutes a promising paradigm for the sustainable recovery of gold, featuring reduced energy consumption, low cost inputs, and the avoidance of environmental pollution. 

Abstract Two-photon excited near-infrared fluorescence materials have garnered considerable attention because of their superior optical penetration, higher spatial resolution, and lower optical scattering compared with other optical materials. Herein, a convenient and efficient supramolecular approach is used to synthesize a two-photon excited near-infrared emissive co-crystalline material. A naphthalenediimide-based triangular macrocycle and coronene form selectively two co-crystals. The triangle-shaped co-crystal emits deep-red fluorescence, while the quadrangle-shaped co-crystal displays deep-red and near-infrared emission centered on 668 nm, which represents a 162 nm red-shift compared with its precursors. Benefiting from intermolecular charge transfer interactions, the two co-crystals possess higher calculated two-photon absorption cross-sections than those of their individual constituents. Their two-photon absorption bands reach into the NIR-II region of the electromagnetic spectrum. The quadrangle-shaped co-crystal constitutes a unique material that exhibits two-photon absorption and near-infrared emission simultaneously. This co-crystallization strategy holds considerable promise for the future design and synthesis of more advanced optical materials. 

Abstract The recognition and separation of anions attracts attention from chemists, materials scientists, and engineers. Employing exo‐binding of artificial macrocycles to selectively recognize anions remains a challenge in supramolecular chemistry. We report the instantaneous co‐crystallization and concomitant co‐precipitation between [PtCl₆]²⁻dianions and cucurbit[6]uril, which relies on the selective recognition of these dianions through noncovalent bonding interactions on the outer surface of cucurbit[6]uril. The selective [PtCl₆]²⁻dianion recognition is driven by weak [Pt−Cl⋅⋅⋅H−C] hydrogen bonding and [Pt−Cl⋅⋅⋅C=O] ion–dipole interactions. The synthetic protocol is highly selective. Recognition is not observed in combinations between cucurbit[6]uril and six other Pt‐ and Pd‐ or Rh‐based chloride anions. We also demonstrated that cucurbit[6]uril is able to separate selectively [PtCl₆]²⁻dianions from a mixture of [PtCl₆]²⁻, [PdCl₄]²⁻, and [RhCl₆]³⁻anions. This protocol could be exploited to recover platinum from spent vehicular three‐way catalytic converters and other platinum‐bearing metal waste. 

Abstract Complexation between a viologen radical cation (V^.+) and cyclobis(paraquat‐p‐phenylene) diradical dication (CBPQT^2(.+)) has been investigated and utilized extensively in the construction of mechanically interlocked molecules (MIMs) and artificial molecular machines (AMMs). The selective recognition of a pair ofV^.+using radical‐pairing interactions, however, remains a formidable challenge. Herein, we report the efficient encapsulation of two methyl viologen radical cations (MV^.+) in a size‐matched bisradical dicationic host — namely, cyclobis(paraquat‐2,6‐naphthalene)^2(.+), i.e.,CBPQN^2(.+). Central to this dual recognition process was the choice of 2,6‐bismethylenenaphthalene linkers for incorporation into the bisradical dicationic host. They provide the space between the two bipyridinium radical cations inCBPQN^2(.+)suitable for binding twoMV^.+with relatively short (3.05–3.25 Å) radical‐pairing distances. The size‐matched bisradical dicationic host was found to exhibit highly selective and cooperative association with the twoMV^.+in MeCN at room temperature. The formation of the tetrakisradical tetracationic inclusion complex — namely, [(MV)₂⊂CBPQN]^4(.+)– in MeCN was confirmed by VT¹H NMR, as well as by EPR spectroscopy. The solid‐state superstructure of [(MV)₂⊂CBPQN]^4(.+)reveals an uneven distribution of the binding distances (3.05, 3.24, 3.05 Å) between the three differentV^.+, suggesting that localization of the radical‐pairing interactions has a strong influence on the packing of the twoMV^.+inside the bisradical dicationic host. Our findings constitute a rare example of binding two radical guests with high affinity and cooperativity using host‐guest radical‐pairing interactions. Moreover, they open up possibilities of harnessing the tetrakisradical tetracationic inclusion complex as a new, orthogonal and redox‐switchable recognition motif for the construction of MIMs and AMMs.