Conspectus Supramolecular self-assembly, which creates the ordered structures as a result of spontaneous organization of building blocks driven by noncovalent interactions (NCIs), is ubiquitous in ...nature. Recently, it has become increasingly clear that nature often builds up complex structures by employing a hierarchical self-assembly (HSA) strategy, in which the components are brought together in a stepwise process via multiple NCIs. Inspired by the dedicated biological structures in nature, HSA has been widely explored to construct well-defined assemblies with increasing complexity. The employment of direct metal–ligand bonds to drive the formation of discrete metallosupramolecular architectures has proven to be a highly efficient strategy to prepare structurally diverse architectures like two-dimensional (2-D) polygons and three-dimensional (3-D) polyhedra with well-defined shapes, sizes, and geometries. Such well-defined organometallic assemblies provide an ideal platform for designing novel artificial supramolecular systems with the increasing complexity though HSA. The presence of a well-defined organometallic scaffold brings an additional dimension to the final nanoscale structures. Moreover, the multilevel dynamic nature of hierarchical self-assemblies brings more structural and functional possibilities of resultant supramolecular systems. This Account will focus on our recent advance on construction of stimuli-responsive functional materials through HSA involving coordination interactions. In our study, a series of functionalized metallacycles were first constructed through coordination-driven self-assembly (CDSA). Then, the secondary noncovalent interaction sites were integrated within the functionalized metallacycle system via either preassembly or postassembly approach. Different segments, such as alkyl chains, dendrimers, cholesteryl moiety, covalent macrocycles, and even polymeric fragments, which could provide hydrophobic and hydrophilic interactions, van der Waals forces, hydrogen bonding, CH−π and π–π interactions, and host–guest interactions, have been utilized to provide the secondary NCIs. Further self-assembly of functionalized metallacycles gives rise to the formation of complex higher-order structures driven by other NCIs by taking advantages of orthogonal property of coordination bonds with other NCIs. By changing the type of additional NCIs embodied in building blocks, different supramolecular architectures, such as the ordered nanostructures, supramolecular polymers and gels, fluorescent materials and sensors, have been successfully prepared with the tailored chemical and physical properties. In particular, the dynamic nature of coordination bonds as well as other NCIs endows final assemblies with stimuli-responsive functions. Collectively, our studies suggest that combining coordination and other NCIs in a well-defined and precise manner is a highly efficient strategy to achieve the complex architectures and functional materials. Therefore, it is very promising to develop the desired functional materials with high precision and fidelity by employing HSA involving coordination interactions.
Polymers have greatly changed and are still changing the way we live ever since, and the construction of novel polymers as functional materials remains an attractive topic in polymer science and ...related areas. During the past few years, the marriage of discrete supramolecular coordination complexes (SCCs), including two-dimensional (2D) metallacycles and three-dimensional (3D) metallacages, and polymers gave rise to two novel types of metallo-supramolecular polymers,
i.e.
, metallacycle/metallacage-cored star polymers (MSPs) and metallacycle/metallacage-crosslinked polymer networks (MPNs), which has attracted increasing attention and emerged as an exciting new research direction in polymer chemistry. Attributed to their well-defined and diverse topological architectures as well as the unique dynamic features of metallacycles/metallacages as cores or crosslinks, these novel polymers have shown extensive applications. In this review, aiming at providing a practical guide to this emerging area, the introduction of synthetic strategies towards MSPs and MPNs will be presented. In addition, their wide applications in areas such as functional materials, molecular sieving, drug delivery, bacterial killing and bioimaging are also discussed.
The marriage of polymerization and coordination-driven self-assembly has given rise to novel types of metallo-supramolecular polymers with well-defined and diverse topological architectures as well as unique dynamic features.
The construction of circularly polarized luminescence (CPL) switches with multiple switchable emission states and high dissymmetry factors (glum) has attracted increasing attention due to their broad ...applications in diverse fields such as the development of smart devices and sensors. Herein, a new family of AIE‐active chiral 3rotaxanes were designed and synthesized, from which a novel CPL switching system was successfully constructed. The switching process was realized through the controlled motions of the chiral pillar5arene macrocycles along the axle through the addition or removal of the acetate anions, which not only modulated the chirality information transfer but also tuned the aggregations of the integrated 3rotaxanes, thus resulting in reversible transformations between two emission states with both high photoluminescence quantum yields (PLQYs) and high dissymmetry factors (glum) values.
The marriage of a switchable rotaxane and an AIEgen gave rise to the successful construction of a novel chiral 3rotaxane‐based CPL switching system with large glum values, remarkable difference in the glum values, and excellent cycling ability.
Over the past few decades, supramolecular chirality in discrete metallosupramolecular architectures has received considerable attention. In this review, a comprehensive summary of discrete, chiral ...coordination-driven structures, including helices, metallacycles, metallocages,
etc.
, is presented. Although chirality can be introduced prior to, during or even after the coordination self-assembly process, this review puts major emphasis on the more recent development of metallosupramolecular architectures from chiral components, where chirality arises from the enantiopure or racemic scaffolds (bridging or auxiliary ligand). Special attention will be paid to homochiral metallo-assemblies using achiral components where chirality is obtained as a consequence of the twisting of the ligands. Additionally, the potential applications of homochiral metallosupramolecular architectures are also discussed. We hope that this review will be of interest to researchers attempting to design new elaborate homochiral metallosupramolecular architectures with even greater complexity and potential for functions such as chiral recognition, enantiomer separation, asymmetric catalysis, nonlinear sensors, and devices.
A comprehensive summary of construction and potential applications of discrete, chiral metallosupramolecular architectures is presented herein.
In this review, a comprehensive summary of supramolecular transformations within discrete coordination-driven supramolecular architectures, including helices, metallacycles, metallacages,
etc.
, is ...presented. Recent investigations have demonstrated that coordination-driven self-assembled architectures provide an ideal platform to study supramolecular transformations mainly due to the relatively rigid yet dynamic nature of the coordination bonds. Various stimuli have been extensively employed to trigger the transformation processes of metallosupramolecular architectures, such as solvents, concentration, anions, guests, change in component fractions or chemical compositions, light, and post-modification reactions, which allowed for the formation of new structures with specific properties and functions. Thus, it is believed that supramolecular transformations could serve as another highly efficient approach for generating diverse metallosupramolecular architectures. Classified by the aforementioned various stimuli used to induce the interconversion processes, the emphasis in this review will be on the transformation conditions, structural changes, mechanisms, and the output of specific properties and functions upon induction of structural transformations.
In this review, a comprehensive summary of supramolecular transformations within discrete coordination-driven supramolecular architectures, including helices, metallacycles, metallacages,
etc.
, is presented.
Aiming at the construction of novel platform for efficient light harvesting, the precise synthesis of a new family of AIEgen‐branched rotaxane dendrimers was successful realized from an ...AIEgen‐functionalized 2rotaxane through a controllable divergent approach. In the resultant AIE macromolecules, up to twenty‐one AIEgens located at the tails of each branches, thus making them the first successful example of AIEgen‐branched dendrimers. Attributed to the solvent‐induced switching feature of the rotaxane branches, the integrated rotaxane dendrimers displayed interesting dynamic feature upon the aggregation‐induced emission (AIE) process. Moreover, novel artificial light‐harvesting systems were further constructed based on these AIEgen‐branched rotaxane dendrimers, which revealed impressive generation‐dependent photocatalytic performances for both photooxidation reaction and aerobic cross‐dehydrogenative coupling (CDC) reaction.
A novel artificial light‐harvesting system based on AIEgen‐branched rotaxane dendrimers has been successfully constructed which displayed impressive generation‐dependent photocatalytic performances for both photooxidation reaction and aerobic cross‐dehydrogenative coupling reaction.
The challenges of developing neuromorphic vision systems inspired by the human eye come not only from how to recreate the flexibility, sophistication, and adaptability of animal systems, but also how ...to do so with computational efficiency and elegance. Similar to biological systems, these neuromorphic circuits integrate functions of image sensing, memory and processing into the device, and process continuous analog brightness signal in real-time. High-integration, flexibility and ultra-sensitivity are essential for practical artificial vision systems that attempt to emulate biological processing. Here, we present a flexible optoelectronic sensor array of 1024 pixels using a combination of carbon nanotubes and perovskite quantum dots as active materials for an efficient neuromorphic vision system. The device has an extraordinary sensitivity to light with a responsivity of 5.1 × 10
A/W and a specific detectivity of 2 × 10
Jones, and demonstrates neuromorphic reinforcement learning by training the sensor array with a weak light pulse of 1 μW/cm
.
Supramolecular radical chemistry has been emerging as a cutting-edge interdisciplinary field of traditional supramolecular chemistry and radical chemistry in recent years. The purpose of such a ...fundamental research field is to combine traditional supramolecular chemistry and radical chemistry together, and take the benefit of both to eventually create new molecules and materials. Recently, supramolecular radical cages have been becoming one of the most frontier and challenging research focuses in the field of supramolecular chemistry. In this
Perspective
, we give a brief introduction to organic radical chemistry, supramolecular chemistry, and the emerging supramolecular radical chemistry along with their history and application. Subsequently, we turn to the main part of this topic: supramolecular radical cages. The design and synthesis of supramolecular cages consisting of redox-active building blocks and radical centres are summarized. The host-guest interactions between supramolecular (radical) cages and organic radicals are also surveyed. Some interesting properties and applications of supramolecular radical cages such as their unique spin-spin interactions and intriguing confinement effects in radical-mediated/catalyzed reactions are comprehensively discussed and highlighted in the main text. The purpose of this
Perspective
is to help students and researchers understand the development of supramolecular radical cages, and potentially to stimulate innovation and creativity and infuse new energy into the fields of traditional supramolecular chemistry and radical chemistry as well as supramolecular radical chemistry.
This
Perspective
summarizes the recent developments of supramolecular radical cages including the design and synthesis of radical cages, their interesting host-guest spin-spin interactions and applications in radical-mediated/catalyzed reactions.
Observations of ultradiffuse galaxies NGC 1052-DF2 and -DF4 show they may contain little dark matter, challenging our understanding of galaxy formation. Using controlled N-body simulations, we ...explore the possibility that their properties can be reproduced through tidal stripping from the elliptical galaxy NGC 1052, in both cold dark matter (CDM) and self-interacting dark matter (SIDM) scenarios. To explain the dark matter deficiency, we find that a CDM halo must have a very low concentration so that it can lose sufficient inner mass in the tidal field. In contrast, SIDM favors a higher and more reasonable concentration as core formation enhances tidal mass loss. Final stellar distributions in our SIDM benchmarks are more diffuse than the CDM one, and hence the former are in better agreement with the data. We further show that a cored CDM halo model modified by strong baryonic feedback is unlikely to reproduce the observations. Our results indicate that SIDM is more favorable for the formation of dark-matter-deficient galaxies.
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