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Deeply electrolytic reduction of carbon dioxide (CO2) to high‐value ethylene (C2H4) is very attractive. However, the sluggish kinetics of C−C coupling seriously results in the low selectivity of CO2 electroreduction to C2H4. Herein, we report a copper‐based polyhedron (Cu2) that features uniformly distributed and atomically precise bi‐Cu units, which can stabilize *OCCO dipole to facilitate the C−C coupling for high selective C2H4 production. The C2H4 faradaic efficiency (FE) reaches 51 % with a current density of 469.4 mA cm−2, much superior to the Cu single site catalyst (Cu SAC) (~0 %). Moreover, the Cu2 catalyst has a higher turnover frequency (TOF, ~520 h−1) compared to Cu nanoparticles (~9.42 h−1) and Cu SAC (~0.87 h−1). In situ characterizations and theoretical calculations revealed that the unique Cu2 structural configuration could optimize the dipole moments and stabilize the *OCCO adsorbate to promote the generation of C2H4. [ABSTRACT FROM AUTHOR]

Deeply electrolytic reduction of carbon dioxide (CO2) to high‐value ethylene (C2H4) is very attractive. However, the sluggish kinetics of C−C coupling seriously results in the low selectivity of CO2 electroreduction to C2H4. Herein, we report a copper‐based polyhedron (Cu2) that features uniformly distributed and atomically precise bi‐Cu units, which can stabilize *OCCO dipole to facilitate the C−C coupling for high selective C2H4 production. The C2H4 faradaic efficiency (FE) reaches 51 % with a current density of 469.4 mA cm−2, much superior to the Cu single site catalyst (Cu SAC) (~0 %). Moreover, the Cu2 catalyst has a higher turnover frequency (TOF, ~520 h−1) compared to Cu nanoparticles (~9.42 h−1) and Cu SAC (~0.87 h−1). In situ characterizations and theoretical calculations revealed that the unique Cu2 structural configuration could optimize the dipole moments and stabilize the *OCCO adsorbate to promote the generation of C2H4. [ABSTRACT FROM AUTHOR]

The high‐resolution X‐ray structures of the model protein lysozyme in the presence of the potential drug [VIVO(acetylacetonato)2] from crystals grown in 1.1 M NaCl, 0.1 M sodium acetate at pH 4.0 reveal the binding to the protein of different and unexpected mixed‐valence cage‐like polyoxidovanadates (POVs): [V15O36(OH2)]5−, which non‐covalently interacts with the lysozyme surface, [V15O33(OH2)]+ and [V20O51(OH2)]n− (this latter based on an unusual {V18O43} cage) which covalently bind the protein. EPR spectroscopy confirms the partial oxidation of VIV to VV and the formation of mixed‐valence species. The results indicate that the interaction with proteins can stabilize the structure of unexpected – both for dimension and architecture – POVs, not observed in aqueous solution. [ABSTRACT FROM AUTHOR]

Exploration of efficient red emitting antimony hybrid halide with large Stokes shift and zero self‐absorption is highly desirable due to its enormous potential for applications in solid light emitting, and active optical waveguides. However, it is still challenging and rarely reported. Herein, a series of (TMS)2SbCl5 (TMS=triphenylsulfonium cation) crystals have been prepared with diverse [SbCl5]2− configurations and distinctive emission color. Among them, cubic‐phase (TMS)2SbCl5 shows bright red emission with a large Stokes shift of 312 nm. In contrast, monoclinic and orthorhombic (TMS)2SbCl5 crystals deliver efficient yellow and orange emission, respectively. Comprehensive structural investigations reveal that larger Stokes shift and longer‐wavelength emission of cubic (TMS)2SbCl5 can be attributed to the larger lattice volume and longer Sb⋅⋅⋅Sb distance, which favor sufficient structural aberration freedom at excited states. Together with robust stability, (TMS)2SbCl5 crystal family has been applied as optical waveguide with ultralow loss coefficient of 3.67 ⋅ 10−4 dB μm−1, and shows superior performance in white‐light emission and anti‐counterfeiting. In short, our study provides a novel and fundamental perspective to structure‐property‐application relationship of antimony hybrid halides, which will contribute to future rational design of high‐performance emissive metal halides. [ABSTRACT FROM AUTHOR]

This article presents a case study on the decomposition reactions of N-heterocyclic carbenes (NHCs) with saturated backbones in the coordination sphere of alanes. The study challenges the common assumption that NHCs are inert spectators and explores their reactivity with different Lewis acids and carbene types. The text discusses the synthesis of various compounds using different routes and analyzes the reactions and products using spectroscopy techniques. The article also discusses the formation of ringer-expanded compounds and the role of different NHC ligands in the reactions. The study provides insights into the reactivity of these compounds and their potential applications. The crystallographic data for the compounds discussed in the study are available for further reference. The research was supported by the Julius-Maximilians-Universität Würzburg and the Deutsche Forschungsgemeinschaft. [Extracted from the article]

Hollow nanoporous carbon architectures (HNCs) present significant utilitarian value for a wide variety of applications. Facile and efficient preparation of HNCs has long been pursued but still remains challenging. Herein, we for the first time demonstrate that single‐component metal–organic frameworks (MOFs) crystals, rather than the widely reported hybrid ones which necessitate tedious operations for preparation, could enable the facile and versatile syntheses of functional HNCs. By controlling the growth kinetics, the MOFs crystals (STU‐1) are readily engineered into different shapes with designated styles of crystalline inhomogeneity. A subsequent one‐step pyrolysis of these MOFs with intraparticle difference can induce a simultaneous self‐hollowing and carbonization process, thereby producing various functional HNCs including yolk‐shell polyhedrons, hollow microspheres, mesoporous architectures, and superstructures. Superior to the existing methods, this synthetic strategy relies only on the complex nature of single‐component MOFs crystals without involving tedious operations like coating, etching, or ligand exchange, making it convenient, efficient, and easy to scale up. An ultra‐stable Na‐ion battery anode is demonstrated by the HNCs with extraordinary cyclability (93 % capacity retention over 8000 cycles), highlighting a high level of functionality of the HNCs. [ABSTRACT FROM AUTHOR]

High‐resolution crystal structures of lysozyme in the presence of the potential drug VIVO(acetylacetonato)2 under two different experimental conditions have been solved. The crystallographic study reveals the loss of the ligands, the oxidation of VIV to VV and the subsequent formation of adducts of the protein with two different polyoxidovanadates: [V4O12]4−, which interacts with lysozyme non‐covalently, and the unprecedented [V20O54(NO3)]n−, which is covalenty bound to the side chain of an aspartate residue of symmetry related molecules. [ABSTRACT FROM AUTHOR]

The precise synthesis of miktoarm star polymers (MSPs) remains one of the great challenges in synthetic chemistry due to the difficulty in locating appropriate structural templates and polymer grafting/growing strategies with high selectivity and efficiency. Herein, ≈2 nm metal‐organic polyhedra (MOPs), constructed from the coordination of isophthalic acid (IPA) and Cu2+, are applied as templates for the precise synthesis of 24‐arm MSPs for their unique logarithmic ligand‐exchange dynamics. Six different polymers are prepared with IPA as an end group and they further coordinated with Cu2+ to afford the corresponding 24‐arm star homo‐polymers. MSPs can be obtained by mixing targeted homo‐arm star polymers in solutions upon thermal annealing. The compositions of MSPs can be facilely and precisely tuned by the recipe of the star polymer mixtures used. Interestingly, the obtained MSPs can be sorted into homo‐arm star polymers through a typical solvent extraction procedure. The hybridization and sorting process can be reversibly conducted through the cycle of thermal annealing and solvent treatment. The complex coordination framework not only opens new avenues for the facile and precise synthesis of MSPs and MOPs with hybrid functionalities, but also provides the capability to design sustainable polymer systems. [ABSTRACT FROM AUTHOR]

The first coordination‐saturated buckyball with a C60 molecule totally encased in an icosidodecahedral Cu30 in a (μ30‐(η2)30)‐fashion, namely C60@Cu30@Cl36N12, has been successfully realized by a C60‐templated assembly. The 48 outmost coordinating atoms (36Cl+12N) comprise a new simple polyhedron that is described by a ccf topology. Charge transfer from (CuI, Cl) to C60 explains the expansion of the light absorption up to 700 nm, and accounts for an ultrafast photophysical process that underpins its high photothermal conversion efficiency. This work makes a giant step forward in exohedral metallofullerene (ExMF) chemistry. [ABSTRACT FROM AUTHOR]

Entangled (M3L2)n polyhedral complexes represent a unique class of supramolecular architectures that are stabilized by relatively weak metal–acetylene interactions in cooperation with conventional metal–pyridyl coordination. Counter‐anion exchange of these complexes with a nitrate (NO3−) ion triggered formal metal insertion between the metal centers, and a heteroleptic ternary coordination mode with acetylenic, pyridyl, and nitrate donors was generated on the metal centers. As a result, the main frameworks of the polyhedral complexes M18L12 and M12L8 were formally extended into a new series of concave polyhedra having the compositions M21L12 and M13L8, respectively. This transformation also resulted in the local disconnection of the highly entangled trifurcate topology of the framework, providing clues toward the skeletal editing of extended and complex three‐dimensional (3D) architectures. [ABSTRACT FROM AUTHOR]

Porous liquids (PLs), a summation of porous hosts and bulky solvents bestowing permanent cavities, are the prominent emerging materials. Despite great efforts, exploration of porous hosts and bulky solvents is still needed to develop new PL systems. Metal‐organic polyhedra (MOPs) with discrete molecular architectures can be considered as porous hosts; however, many of them are insoluble entities. Here we report the transformation of type III PL to type II PLs by tuning the surface rigidity of insoluble MOP, Rh24L24, in a bulky ionic liquid (IL). Functionalization of N‐donor molecules on Rh−Rh axial sites ensue their solubilization in bulky IL which confer type II PLs. Experimental and theoretical studies reveal the bulkiness of IL as per the cage apertures, and the cause of their dissolution as well. The obtained PLs, capturing more CO2 than neat solvent, have depicted higher catalytic activity for CO2 cycloaddition compared to individual MOPs and IL. [ABSTRACT FROM AUTHOR]

It is important to establish and clarify the relationship between stereochemically active lone pairs and birefringence, since it is one of the significantly effective routes to explore birefringent crystals by introducing Sn‐centered polyhedra with stereochemically active lone pairs. Herein, four tin(II)‐based ternary halides A3SnCl5 and ASn2Cl5 (A=NH4 and Rb) have been synthesized successfully. The experimental birefringence of Rb3SnCl5 and RbSn2Cl5 is larger than or equal to 0.046 and 0.123@546 nm, respectively. Through investigating the alkali or alkaline‐earth metal tin(II)‐based ternary halides, the structure‐performance relationship has been concluded between stereochemically active lone pairs and optical anisotropy. It is beneficial to the analysis and prediction of birefringence in tin‐based halides and provides a guide for exploring tin(II)‐based optoelectronic functional materials. [ABSTRACT FROM AUTHOR]

Fractal structures with self‐similarity are of fundamental importance in the fields of aesthetic, chemistry and mathematics. Here, by taking advantage of constructs the rational geometry‐directed precursor design, we report the construction of two fascinating Platonic solids, the Sierpiński tetrahedron ST‐T and the Sierpiński octahedron ST‐O, in which each possesses a fractal Sierpiński triangle on their independent faces. These two discrete complexes are formed in near‐quantitative yield from the multi‐component self‐assembly of truncated Sierpiński triangular kernel L1 with tribenzotriquinacene‐based hexatopic and anthracene‐based tetratopic terpyridine ligands (L3 and L4) in the presence of metal ions, respectively. The enhanced stabilities of the 3D discrete structures were investigated by gradient tandem mass spectrometry (gMS2). This work provides new constructs for the imitation of complex virus assemblies and for the molecular encapsulation of giant guest molecules. [ABSTRACT FROM AUTHOR]

A porous liquid is a unique liquid medium that combines the cavity of porous solids with the fluidity of liquids. This special characteristic offers potential in various applications. Here we report a type II photoresponsive porous ionic liquid (PPIL) from dissolving a photoresponsive metal‐organic polyhedron (PMOP, constructed from dicopper and azobenzene‐containing carboxylate) in a polyethylene‐glycol‐functionalized bulky ionic liquid (IL). Owing to favorable ion interactions, bulky IL molecules encircle outside PMOP, and the inter cavities are maintained. The azobenzene moieties can be isomerized freely in the PPILs to expose and shelter active sites upon visible and UV light irradiation. Hence, the adsorption capacity of PPILs is controllable by light irradiation, and the change in CO2 uptake is up to 30 % compared to neat IL. This study may inspire the development of new adsorption process regulated by light instead of pressure and temperature swing adsorption. [ABSTRACT FROM AUTHOR]

Porous supramolecular assemblies constructed by noncovalent interactions are promising for adsorptive purification of methane because of their easy regeneration. However, the poor stability arising from the weak noncovalent interactions has obstructed their practical applications. Here, we report a robust and easily regenerated polyhedron‐based cationic framework assembled from a metal–organic square. This material exhibits a very low affinity for CH4 and N2, but captures other competing gases (e.g. C2H6, C3H8, and CO2) with a moderate affinity. These results underpin highly selective separation of a range of gas mixtures that are relevant to natural gas and industrial off‐gas. Dynamic breakthrough studies demonstrate its practical separation for C2H6/CH4, C3H8/CH4, CO2/N2, and CO2/CH4. Particularly, the separation time is ≈11 min g−1 for the C2H6/CH4 (15/85 v/v) mixture and ≈49 min g−1 for the C3H8/CH4 (15/85 v/v) mixture (under a flow of 2.0 mL min−1), respectively, enabling its capability for CH4 purification from light alkanes. [ABSTRACT FROM AUTHOR]

Coordination‐driven crosslinking networks with reversible and dynamic characteristics are gaining increasing interest in diverse application fields. Herein, we use a coordination crosslinking approach using metal‐organic polyhedra (MOPs) as high‐connectivity building blocks to post‐assemble a class of coordination hypercrosslinked MOP (CHMOP) polymers. The introduction of 12‐connected MOP nodes to the polymeric networks is critical to producing membranes that overcome the trade‐off between mechanical properties and dynamic healing, and meanwhile possess multifunctionalities including shape memory, solution processability, and 3D printing. The CHMOPs can also be used for anticorrosion coating and achieve function couplings, e.g. shape memory‐assisted self‐healing (SMASH), which have not been achieved in the MOP‐based hybrid materials yet. This work not only offers a feasible strategy to construct new multifunctional materials but also greatly expands the application scopes of MOPs. [ABSTRACT FROM AUTHOR]

Two structurally intricate heterometallic clusters with cores featuring multiple Platonic and Archimedean polyhedra were synthesized by ligand‐controlled co‐hydrolysis of Ni2+ and Dy3+ ions, as reported by Zhiping Zheng et al. in their Research Article (e202409109). Adjusting the amount of hydrolysis‐promoting base and the reaction temperature and duration afforded selectively the kinetic and thermodynamic species, respectively with a Dy112Ni76 and a Dy52Ni44 core...By Na Xu; Wanmin Chen; Jun Miao; Yousong Ding and Zhiping ZhengReported by Author; Author; Author; Author; Author [Extracted from the article]

This article, published in Angewandte Chemie, highlights several research findings in the field of chemistry. The first study by Nishant Singh and co-workers explores how amino acid droplets can transform into poly-crystals and fibrous hydrogels through complex pathways. Another study by Peter J. Stang and colleagues focuses on a NIR-light-activated and lysosomal-targeted PtII metallacycle that enhances cancer immunotherapy. Zhen Gu and Jicheng Yu demonstrate a method for engineering platelet-drug conjugates for efficient and safe drug delivery. Zhiping Zheng and his team synthesized heterometallic clusters with intricate structures, and Tomislav Friščić and his colleagues used halogen bonding to recognize carbon-only molecular fragments. [Extracted from the article]

A tritopic, Ni‐substituted Keggin cluster, {SiW9Ni4}, assembles with rigid dicarboxylate linkers to give rise to a set of discrete, POM2nL3n‐type structures (POM={SiW9Ni4}) with defined interior voids. The outcome of coordination‐driven self‐assemblies of these polyhedral cages—from fused dimers to trigonal prisms—was found to be sensitive to bend angles of the ditopic ligands, which vary from 122° to 180°. These polyoxotungstate‐based metal–organic polyhedra, when coupled with [Ru(bpy)3]Cl2 as a photosensitizer and triethanolamine as the electron donor, serve as highly effective catalysts for CO2 reduction, with turnover numbers up to 328 and CO selectivity as high as 96.2 %. The inner cavities of such cage structures, if functionalized or of sufficient size to encapsulate targeted guest molecules, could present a new strategy towards functional materials for potential applications. [ABSTRACT FROM AUTHOR]

Pd‐based molecular square Pd4L4 and triangle Pd3L3 represent the molecular ancestors of metal‐coordination polyhedra that have been an integral part of the field for the last 30 years. Conventional solution‐based reactions between cis‐protected Pd ions and 2,2′‐bipyridine exclusively give Pd4L4 and/or Pd3L3 as the sole products. We herein show that, under solvent‐free mechanochemical conditions, the self‐assembly energy landscape can be thermodynamically manipulated to form an elusive cyclic dimer Pd2L2 for the first time. In the absence of solvent, Pd2L2 is indefinitely stable in the solid‐state, but converts rapidly to its thermodynamic products Pd3L3 and Pd4L4 in solution, confirming Pd2L2 as a short‐lived kinetic species in the solution‐based self‐assembly process. Our results highlight how mechanochemistry grants access to a vastly different chemical space than available under conventional solution conditions. This provides a unique opportunity to isolate elusive species in self‐assembly processes that are too reactive to both "see" and "capture". [ABSTRACT FROM AUTHOR]

Pd‐based molecular square Pd4L4 and triangle Pd3L3 represent the molecular ancestors of metal‐coordination polyhedra that have been an integral part of the field for the last 30 years. Conventional solution‐based reactions between cis‐protected Pd ions and 2,2′‐bipyridine exclusively give Pd4L4 and/or Pd3L3 as the sole products. We herein show that, under solvent‐free mechanochemical conditions, the self‐assembly energy landscape can be thermodynamically manipulated to form an elusive cyclic dimer Pd2L2 for the first time. In the absence of solvent, Pd2L2 is indefinitely stable in the solid‐state, but converts rapidly to its thermodynamic products Pd3L3 and Pd4L4 in solution, confirming Pd2L2 as a short‐lived kinetic species in the solution‐based self‐assembly process. Our results highlight how mechanochemistry grants access to a vastly different chemical space than available under conventional solution conditions. This provides a unique opportunity to isolate elusive species in self‐assembly processes that are too reactive to both "see" and "capture". [ABSTRACT FROM AUTHOR]

The targeted synthesis of deep‐ultraviolet (deep‐UV) nonlinear optical (NLO) materials, especially those with non‐π‐conjugated sulfates, has experienced considerable difficulties due to the need to reconcile the oft‐competing requirements for deep‐UV transparency and strong second‐harmonic generation (SHG). We report herein the designed synthesis of the first rare‐earth metal‐based deep‐UV sulfate La(NH4)(SO4)2 by a double‐salt strategy involving introduction of complementary cations, together with optical studies that reveal a short‐wavelength deep‐UV absorption edge (below 190 nm) and the strongest SHG response among deep‐UV NLO sulfates (2.4×KDP). Theoretical calculations and crystal structure analysis suggest that the excellent balance between SHG response and deep‐UV transparency can be attributed to a synergistic interaction of the hetero‐cations La3+ and [NH4]+, which optimize alignment of the [SO4] tetrahedra and highly polarizable [LaO8] polyhedra. [ABSTRACT FROM AUTHOR]

Bond breaking is an essential process in chemical transformations and the ability of researchers to strategically dictate which bonds in a given system will be broken translates to greater synthetic control. Here, we report extending the concept of selective bond breaking to reticular materials in a new synthetic approach that we call Clip‐off Chemistry. We show that bond‐breaking in these structures can be controlled at the molecular level; is periodic, quantitative, and selective; is effective in reactions performed in either solid or liquid phases; and can occur in a single‐crystal‐to‐single‐crystal fashion involving the entire bulk precursor sample. We validate Clip‐off Chemistry by synthesizing two topologically distinct 3D metal‐organic frameworks (MOFs) from two reported 3D MOFs, and a metal‐organic macrocycle from metal‐organic polyhedra (MOP). Clip‐off Chemistry opens the door to the programmed disassembly of reticular materials and thus to the design and synthesis of new molecules and materials. [ABSTRACT FROM AUTHOR]

Study of mid‐infrared (mid‐IR) nonlinear optical (NLO) materials is hindered by the competing requirements of optimized second‐harmonic generation (SHG) coefficient dij and laser‐induced damage threshold (LIDT) as well as the harsh synthetic conditions. Herein, we report facile hydrothermal synthesis of a polar NLO vanadate Cs4V8O22 (CVO) featuring a quasi‐rigid honeycomb‐layered structure with [VO4] and [VO5] polyhedra aligned parallel. CVO possesses a wide IR‐transparent window, high LIDT, and congruent‐melting behavior. It has very strong phase‐matchable SHG intensities in metal vanadate family (12.0 × KDP @ 1064 nm and 2.2 × AGS @ 2100 nm). First‐principles calculations suggest that the exceptional SHG responses of CVO largely originate from virtual electronic transitions within [V4O11]∞ layer; the excellent optical transmittance of CVO arises from the special characteristics of vibrational phonons resulting from the layered structure. [ABSTRACT FROM AUTHOR]

The physicochemical similarity of isomers makes their chemical separation through conventional techniques energy intensive. Herein, we report that, instead of using traditional encapsulation‐driven processes, steric hindrance in metal coordination on the outer surface of RhII‐based metal–organic polyhedra (Rh‐MOPs) can be used to separate pyridine‐based regioisomers via liquid–liquid extraction. Through molecular dynamics simulations and wet experiments, we discovered that the capacity of pyridines to coordinatively bind to Rh‐MOPs is determined by the positions of the pyridine substituents relative to the pyridine nitrogen and is influenced by steric hindrance. Thus, we exploited the differential solubility of bound and non‐bound pyridine regioisomers to engineer liquid–liquid self‐sorting systems. As a proof of concept, we separated four different equimolecular mixtures of regioisomers, including a mixture of the industrially relevant compounds 2‐chloropyridine and 3‐chloropyridine, isolating highly pure compounds in all cases. [ABSTRACT FROM AUTHOR]

Use of preformed metal‐organic polyhedra (MOPs) as supermolecular building blocks (SBBs) for the synthesis of metal‐organic frameworks (MOFs) remains underexplored due to lack of robust functionalized MOPs. Herein we report the use of polycarboxylate cuboctahedral RhII‐MOPs for constructing highly‐connected MOFs. Cuboctahedral MOPs were functionalized with carboxylic acid groups on their 12 vertices or 24 edges through coordinative or covalent post‐synthetic routes, respectively. We then used each isolated polycarboxylate RhII‐MOP as 12‐c cuboctahedral or 24‐c rhombicuboctahedral SBBs that, upon linkage with metallic secondary building units (SBUs), afford bimetallic highly‐connected MOFs. The assembly of a pre‐synthesized 12‐c SBB with a 4‐c paddle‐wheel SBU, and a 24‐c SBB with a 3‐c triangular CuII SBU gave rise to bimetallic MOFs having ftw (4,12)‐c or rht (3,24)‐c topologies, respectively. [ABSTRACT FROM AUTHOR]

The simple binary fluoride α‐SnF2 is shown to be an excellent birefringent material with outstanding birefringence, about 14 times that of MgF2. Furthermore, it exhibits a shorter UV cutoff edge and easy crystal growth at ambient temperature compared to YVO4 and TiO2. A novel theoretical calculation mode was established to analyze the stereochemical‐activity lone‐pair (SCALP) contribution to the birefringence (SCB) based on the SCALP′s strength and arrangement, and it was found that the large birefringence of α‐SnF2 mainly benefits from well‐aligned [SnF5] polyhedra with a strong SCALP. The exploration of the α‐SnF2 birefringent crystal points out the direction of the future search for excellent birefringent materials. [ABSTRACT FROM AUTHOR]

Systematic design and self‐assembly of metal–organic polyhedra with predictable configurations has been a long‐standing challenge in crystal engineering. Herein a concave polyoxovanadate cluster, [V6O6(OCH3)9(SO4)4]5−, which can be generated in situ under specific reaction conditions, is reported. Based on this cluster, a potential trivalent molecular building block, [V6O6(OCH3)9(SO4)(CO2)3]2−, can be obtained by the bridging‐ligand‐substitution strategy and it possesses appropriate angle information for the design of molecular cubes. Utilizing the face‐directed assembly of the trivalent molecular building block and a diverse set of tetratopic carboxylate linkers, a series of metal–organic cubes (VMOC‐1–VMOC‐5) with the same topology but different functionalities and dimensions were designed and constructed. An inclusion study using VMOC‐3 shows that they are potential molecular receptors for selective capture of size‐matching polycyclic aromatic hydrocarbon guest molecules. [ABSTRACT FROM AUTHOR]

In nanoparticle self‐assembly, the current lack of strategy to modulate orientational order creates challenges in isolating large‐area plastic crystals. Here, we achieve two orientationally distinct supercrystals using one nanoparticle shape, including plastic crystals and uniform metacrystals. Our approach integrates multi‐faceted Archimedean polyhedra with molecular‐level surface polymeric interactions to tune nanoparticle orientational order during self‐assembly. Experiments and simulations show that coiled surface polymer chains limit interparticle interactions, creating various geometrical configurations among Archimedean polyhedra to form plastic crystals. In contrast, brush‐like polymer chains enable molecular interdigitation between neighboring particles, favoring consistent particle configurations and result in uniform metacrystals. Our strategy enhances supercrystal diversity for polyhedra comprising multiple nondegenerate facets. [ABSTRACT FROM AUTHOR]

The ability to incorporate functional metal ions (Mn+) into metal–organic coordination complexes adds remarkable flexibility in the synthesis of multifunctional organic–inorganic hybrid materials with tailorable electronic, optical, and magnetic properties. We report the cation‐exchanged synthesis of a diverse range of hollow Mn+‐phytate (PA) micropolyhedra via the use of hollow Co2+‐PA polyhedral networks as templates at room temperature. The attributes of the incoming Mn+, namely Lewis acidity and ionic radius, control the exchange of the parent Co2+ ions and the degree of morphological deformation of the resulting hollow micropolyhedra. New functions can be obtained for both completely and partially exchanged products, as supported by the observation of Ln3+ (Ln3+=Tb3+, Eu3+, and Sm3+) luminescence from as‐prepared hollow Ln3+‐PA micropolyhedra after surface modification with dipicolinic acid as an antenna. Moreover, Fe3+‐ and Mn2+‐PA polyhedral complexes were employed as magnetic contrast agents. [ABSTRACT FROM AUTHOR]

When components of a metal–organic framework (MOF) and a crystal growth modulator diffuse through a gel medium, they can form arrays of regularly‐spaced precipitation bands containing MOF crystals of different morphologies. With time, slow variations in the local concentrations of the growth modulator cause the crystals to change their shapes, ultimately resulting in unusual concave microcrystallites not available via solution‐based methods. The reaction–diffusion and periodic precipitation phenomena 1) extend to various types of MOFs and also MOPs (metal–organic polyhedra), and 2) can be multiplexed to realize within one gel multiple growth conditions, in effect leading to various crystalline phases or polycrystalline formations. [ABSTRACT FROM AUTHOR]

The self‐assembly of nanostructures is dominated by a limited number of strong coordination elements. Herein, we show that metal–acetylene π‐coordination of a tripodal ligand (L) with acetylene spacers gave an M3L2 double‐propeller motif (M=CuI or AgI), which dimerized into an M6L4 interlocked cage (M=CuI). Higher (M3L2)n oligomers were also selectively obtained: an M12L8 truncated tetrahedron (M=CuI) and an M18L12 truncated trigonal prism (M=AgI), both of which contain the same double‐propeller motif. The higher oligomers exhibit multiply entangled facial structures that are classified as a trefoil knot and a Solomon link. The inner cavities of the structures encapsulate counteranions, revealing a potential new strategy towards the synthesis of functional hollow structures that is powered by molecular entanglements. [ABSTRACT FROM AUTHOR]

The excellent birefringent materials are needed for optical systems. Herein, we reported a new compound, the first tin borate chloride, Sn2B5O9Cl (SBOC) with a large birefringence (0.168 at 546 nm) measured by the polarizing microscope. Its birefringence is 16 times that of the isostructural Ba2B5O9Cl (BBOC) compound (0.010@ at 546 nm). The results show that the birefringence enhancement originates mainly from the Sn2+ polyhedra. We propose that the birefringence can be enlarged by substituting the alkaline‐earth metal cation by the Sn2+ cation in the isostructural borate with small birefringence. This strategy will guide the discovery of large birefringent materials in the future. [ABSTRACT FROM AUTHOR]

Monodispersed hairy nanocomposites with typical 2 nm (isophthalic acid)24Cu24 metal–organic polyhedra (MOP) as a core protected by 24 polymer chains with controlled narrow molecular weight distribution has been probed by imaging and scattering studies for the heterogeneity of polymers in the nanocomposites and the confinement effect the MOPs imposing on anchored polymers. Typical confined‐extending surrounded by one entanglement area is proposed to describe the physical states of the polymer chains. This model dictates the counterintuitive thermal and rheological properties and prohibited solvent exchange properties of the nanocomposites, whilst those polymer chain states are tunable and deterministic based on their component inputs. From the relationship between the structure and behavior of the MOP nanocomposites, a MOP‐composited thermoplastic elastomer was obtained, providing practical solutions to improve mechanical/rheological performances and processabilities of inorganic MOPs. [ABSTRACT FROM AUTHOR]

A cesium bismuth germanate, Cs2Bi2O(Ge2O7) (CBGO), was synthesized by a traditional high‐temperature solid‐state reaction. Its structure features a 3D network composed of a 1D chains composed of Bi2O8 dimers that are further bridged by Ge2O7 dimers, forming tunnels of seven member rings (MRs) that are filled by the Cs+ cations. CBGO exhibits extraordinary larger second harmonic generation (SHG) response of about 13.7 times that of KDP (KH2PO4) under 1064 nm laser radiation and 1.1 times that of KTP (KTiOPO4) under 2.05 μm laser radiation, which is the highest among all of the metal germanates reported so far. CBGO possesses a moderate birefringence (0.073 at 1064 nm) and is phase matchable. Furthermore, CBGO melts congruently and exhibits high thermal stability. [ABSTRACT FROM AUTHOR]

Establishing an effective design principle in solid‐state materials for a blue‐light‐excited Eu2+‐doped red‐emitting oxide‐based phosphors remains one of the significant challenges for white light‐emitting diodes (WLEDs). Selective occupation of Eu2+ in inorganic polyhedra with small coordination numbers results in broad‐band red emission as a result of enhanced crystal‐field splitting of 5d levels. Rb3YSi2O7:Eu exhibits a broad emission band at λmax=622 nm under 450 nm excitation, and structural analysis and DFT calculations support the concept that Eu2+ ions preferably occupy RbO6 and YO6 polyhedra and show the characteristic red emission band of Eu2+. The excellent thermal quenching resistance, high color‐rendering index Ra (93), and low CCT (4013 K) of the WLEDs clearly demonstrate that site engineering of rare‐earth phosphors is an effective strategy to target tailored optical performance. [ABSTRACT FROM AUTHOR]

Porous molecular cages have a characteristic processability arising from their solubility, which allows their incorporation into porous materials. Attaining solubility often requires covalently bound functional groups that are unnecessary for porosity and which ultimately occupy free volume in the materials, decreasing their surface areas. Here, a method is described that takes advantage of the coordination bonds in metal–organic polyhedra (MOPs) to render insoluble MOPs soluble by reversibly attaching an alkyl‐functionalized ligand. We then use the newly soluble MOPs as monomers for supramolecular polymerization reactions, obtaining permanently porous, amorphous polymers with the shape of colloids and gels, which display increased gas uptake in comparison with materials made with covalently functionalized MOPs. [ABSTRACT FROM AUTHOR]

Design and synthesis of metal–organic polyhedra (MOPs) with targeted geometries from predetermined secondary building units (SBUs) is a long‐standing challenge in chemistry and material science. Theoretical prediction shows that there are 6 possible polyhedra from the 3‐coordinated, 4‐coordinated octahedron ((3,4)‐c octahedron) to (3,5)‐c icosahedron with minimal transitivity (simplest possible). Except for one missing polyhedron (mtr) due to the unfavorable angles, we report five MOPs based on these structures, including an octahedral (3,4)‐c VMOP‐21 (rdo), an icosahedral (3,5)‐c VMOP‐25 (trc), and three intermediate derived trinodal (3,4,5)‐c VMOP‐22–24 (ghm, hmg, xum). Remarkably, all these MOPs obey the minimal transitivity principle and are consistent with geometrical predictions. [ABSTRACT FROM AUTHOR]

This article, published in the journal Angewandte Chemie, discusses the crystal structures of two adducts formed by the drug VIVO(acetylacetonato)2 with lysozyme. The data shows that the V compound undergoes ligand exchange and oxidation, resulting in the formation of two polyoxidovanadates: [V4O12]4−, which interacts with the protein non-covalently, and [V20O54(NO3)]n−, which is covalently bound to Asp side chains. The findings provide insights into the potential use of vanadium-based drugs for the treatment of diabetes and cancer. [Extracted from the article]

This article, published in Angewandte Chemie, discusses the challenges and potential solutions in the synthesis of miktoarm star polymers. The authors, Mingxin Zhang, Panchao Yin, and their colleagues, propose the use of metal-organic polyhedra with logarithmic ligand exchange dynamics as templates for the reversible sorting and hybridization of miktoarm star polymers. This approach opens up new possibilities for the design of sustainable polymers. The article also briefly mentions other research topics such as visible-light photoswitchable benzimidazole azo-arenes, enantioselective synthesis of arylglycines, electrochemical diacetoxylation of alkenes, and the control of structural properties in supported/bulk metal oxides through catalyst post-treatment. [Extracted from the article]

Abstract: Protein‐based nanoparticles hold promise for a broad range of applications. Here, we report the production of a uniform anionic hollow protein nanoparticle, designated TIP60, which spontaneously assembles from a designed fusion protein subunit based on the geometric features of polyhedra. We show that TIP60 tolerates mutation and both its interior and exterior surfaces can be chemically modified. Moreover, TIP60 forms larger structures upon the addition of a cationic protein. Therefore, TIP60 can be used as a modifiable nano‐building block for further molecular assembly. [ABSTRACT FROM AUTHOR]

Abstract: We have designed and synthesized novel hollow Ni/Fe layered double hydroxide (LDH) polyhedrons as an advanced sulfur host for enhancing the performance of lithium–sulfur (Li–S) batteries. The Ni/Fe LDH host shows multiple advantages. First, the Ni/Fe LDH shells can provide sufficient sulfiphilic sites for chemically bonding with polysulfides. Second, the hollow architecture can provide sufficient inner space for both loading a large amount of sulfur and accommodating its large volumetric expansion. Moreover, once the active material is confined within the host, the shells could easily restrict the outward diffusion of polysulfides, guaranteeing prolonged cycle life even with high sulfur loading. As a result, the S@Ni/Fe LDH cathode has successfully solved the main issues related to sulfur electrodes, and it exhibits significantly improved electrochemical performances with prolonged life over 1000 cycles and excellent rate properties. [ABSTRACT FROM AUTHOR]

This document, published in the journal Angewandte Chemie, discusses various research articles in the field of chemistry. One article explores the use of bond scission as a synthetic tool to design new molecules and materials, showcasing the synthesis of Rh(II)-based architectures through the disassembly of metal-organic polyhedra. Another article focuses on the incorporation of Pd nanoparticles into MOFs for high selectivity in CO esterification. Additionally, there is a report on the use of sulfonium salt reagents for introducing deuterated alkyl groups in drug discovery, and a study on adaptive catalysts that can switch selectivity in hydrogenation reactions. Lastly, the document mentions a research article on the photophysics of [Ru(bpy)3]2+, highlighting the importance of rate-determining states in understanding its behavior. [Extracted from the article]

Based on their structural similarity to natural nucleobases, nucleoside analogue therapeutics were integrated into DNA strands through conventional solid-phase synthesis. By elaborately designing their sequences, floxuridine-integrated DNA strands were synthesized and self-assembled into well-defined DNA polyhedra with definite drug-loading ratios as well as tunable size and morphology. As a novel drug delivery system, these drug-containing DNA polyhedra could ideally mimic the Trojan Horse to deliver chemotherapeutics into tumor cells and fight against cancer. Both in vitro and in vivo results demonstrate that the DNA Trojan horse with buckyball architecture exhibits superior anticancer capability over the free drug and other formulations. With precise control over the drug-loading ratio and structure of the nanocarriers, the DNA Trojan horse may play an important role in anticancer treatment and exhibit great potential in translational nanomedicine. [ABSTRACT FROM AUTHOR]

Keywords: Coordination Polyhedra; Entanglements; Interconversion; Silver Complex; Supramolecular Chemistry EN Coordination Polyhedra Entanglements Interconversion Silver Complex Supramolecular Chemistry 1 1 1 08/09/23 20230814 NES 230814 B Silver-acetylene interactions b adopting a heteroleptic ternary coordination mode enabled the synthesis of concave polyhedral cages upon anion-exchange-triggered interconversion of highly entangled polyhedra. In their Communication (e202303714), Yuya Domoto and co-workers describe skeletally edited 3D architectures having partially disconnected knot or link motifs at their polyhedral faces. Coordination Polyhedra, Entanglements, Interconversion, Silver Complex, Supramolecular Chemistry. [Extracted from the article]

A low-temperature topochemical reduction strategy is used herein to prepare unconventional phosphors with luminescence covering the biological and/or telecommunications optical windows. This approach is demonstrated by using BiIII-doped Y2O3 (Y2− xBi xO3) as a model system. Experimental results suggest that topochemical treatment of Y2− xBi xO3 using CaH2 creates randomly distributed oxygen vacancies in the matrix, resulting in the change of the oxidation states of Bi to lower oxidation states. The change of the Bi coordination environments from the [BiO6] octahedra in Y2− xBi xO3 to the oxygen-deficient [BiO6− z] polyhedra in reduced phases leads to a shift of the emission maximum from the visible to the near-infrared region. The generality of this approach was further demonstrated with other phosphors. Our findings suggest that this strategy can be used to explore Bi-doped or other classes of luminescent systems, thus opening up new avenues to develop novel optical materials. [ABSTRACT FROM AUTHOR]

Development of efficient and affordable electrocatalysts in neutral solutions is paramount importance for the renewable energy. Herein, we report that the oxygen evolution reaction (OER) performance of Co3S4 under neutral conditions can be enhanced by exposed octahedral planes and self-adapted spin states in atomically thin nanosheets. A HAADF image clearly confirmed that the active octahedra with Jahn-Teller distortions were exposed exclusively. Most importantly, in the atomically thin nanosheets, the spin states of Co3+ in the octahedral self-adapt from low-spin to high-spin states. As a result, the synergistic effect endow the Co3S4 nanosheets with superior OER performance, with exceptional low onset overpotentials of circa 0.31 V in neutral solutions, which is state-of-the-art among inorganic non-noble metal compounds. [ABSTRACT FROM AUTHOR]

Inspiration for molecular design and construction can be derived from mathematically based structures. In the quest for new materials, the adaptation of new building blocks can lead to unexpected results. Towards these ends, the quantitative single-step self-assembly of a shape-persistent, Archimedean-based building block, which generates the largest molecular sphere (a cuboctahedron) that has been unequivocally characterized by synchrotron X-ray analysis, is described. The unique properties of this new construct give rise to a dilution-based transformation into two identical spheres (octahedra) each possessing one half of the molecular weight of the parent structure; concentration of this octahedron reconstitutes the original cuboctahedron. These chemical phenomena are reminiscent of biological fission and fusion processes. The large 6 nm cage structure was further analyzed by 1D and 2D NMR spectroscopy, mass spectrometry, and collision cross-section analysis. New routes to molecular encapsulation can be envisioned. [ABSTRACT FROM AUTHOR]

Metal-organic polyhedra (MOPs) or frameworks (MOFs) based on Cr3+ are notoriously difficult to synthesize, especially as crystals large enough to be suitable for characterization of the structure or properties. It is now shown that the co-existence of In3+ and Cr3+ induces a rapid crystal growth of large single crystals of heterometallic In-Cr-MOPs with the [M8L12] (M=In/Cr, L=dinegative 4,5-imidazole-dicarboxylate) cubane-like structure. With a high concentration of protons from 12 carboxyl groups decorating every edge of the cube and an extensive H-bonded network between cubes and surrounding H2O molecules, the newly synthesized In-Cr-MOPs exhibit an exceptionally high proton conductivity (up to 5.8×10−2 S cm−1 at 22.5 °C and 98 % relative humidity, single crystal). [ABSTRACT FROM AUTHOR]

Shape-persistent covalent organic polyhedrons (COPs) with ethynylene linkers are usually prepared through kinetically controlled cross-coupling reactions. The high-yielding synthesis of ethynylene-linked rigid tetrameric cages via one-step alkyne metathesis from readily accessible triyne precursors is presented. The tetrameric cage contains two macrocyclic panels and exhibits D2 h symmetry. The assembly of such a COP is a thermodynamically controlled process, which involves the initial formation of macrocycles as key intermediates followed by the connection of two macrocycles with ethynylene linkages. With a large internal cavity, the cage exhibits a high binding selectivity toward C70 ( K=3.9×103 L mol−1) over C60 (no noticeable binding). [ABSTRACT FROM AUTHOR]