Solvent-Mediated Hetero/Homo-Phase Crystallization of Copper Nanoclusters and Superatomic Kernel-Related NIR Phosphorescence.

Atomically precise superatomic copper nanoclusters (Cu NCs) have been the subject of immense interest for their intriguing structures and diverse properties; nonetheless, the variable oxidation state of copper ions and complex solvation effects in wet synthesis systems pose significant challenges for comprehending their synthesis and crystallization mechanism. Herein, we present a solvent-mediated approach for the synthesis of two Cu NCs, namely, superatomic Cu26 and pure-Cu(I) Cu16. They initially formed as a hetero-phase and then separated as a homo-phase via modulating binary solvent composition. In situ UV/vis absorption and electrospray ionization mass spectra revealed that the solvent-mediated assembly was determined to be the underlying mechanism of hetero/homo-phase crystallization. Cu26 is a 2-electron superatom with a kernel-shell structure that includes a [Cu20Se12]4- shell and [Cu6]4+ kernel, containing two 1S jellium electrons. Conversely, Cu16 is a pure-Cu(I) Cu/Se nanocluster that features a [Cu16Se6]4+ core protected by extra dimercaptomaleonitrile ligands. Remarkably, Cu26 exhibits unique near-infrared phosphorescence (NIR PH) at 933 nm due to the presence of a superatomic kernel-related charge transfer state (3MM(Cu)CT). Overall, this work not only showcases the hetero/homo-phase crystallization of Cu NCs driven by a solvent-mediated assembly mechanism but also enables the rare occurrence of NIR PH within the 2-electron copper superatom family.

Temperature-Controlled Selective Formation of Silver Nanoclusters and Their Transformation to the Same Product.

Herein, two atomically precise silver nanoclusters, Ag54 and Ag33, directed by inner anion templates (CrO4 2- and/or Cl-), are initially isolated as a mixed phase from identical reactants across a wide temperature range (20-80 °C). Interestingly, fine-tuning the reaction temperature can realize pure phase synthesis of the two nanoclusters; that is, a metastable Ag54 is kinetically formed at a low temperature (20 °C), whereas such a system is steered towards a thermodynamically stable Ag33 at a relatively high temperature (80 °C). Electrospray ionization mass spectrometry illustrates that the stability of Ag33 is superior to that of Ag54, which is further supported by density functional theory calculations. Importantly, the difference in structural stability can influence the pathway of 1,4-bis(pyrid-4-yl)benzene induced transformation reaction starting from Ag54 and Ag33. The former undergoes a dramatic breakage-reorganization process to form an Ag31 dimer (Ag31), while the same product can be also achieved from the latter following a noninvasive ligand exchange process. Both the Ag54 and Ag33 have the potential for further remote laser ignition applications. This work not only demonstrates how temperature controls the isolation of a specific phase, but also sheds light on the structural transformation pathway of nanoclusters with different stability.

Dynamic and transformable Cu12 cluster-based C-H···π-stacked porous supramolecular frameworks.

The assembly of cluster-based π-stacked porous supramolecular frameworks presents daunting challenges, including the design of suitable cluster building units, control of the sufficient C-H···π interactions, trade-off between structural dynamics and stability as well as understanding the resulting collective properties. Herein, we report a cluster-based C-H···π interaction-stacked porous supramolecular framework, namely, Cu12a-π, consisting of Cu12 nanocluster as a 6-connected node, which is further propagated to a dynamic porous supramolecular frameworks via dense intralayer C-H···π interactions, yielding permanent porosity. In addition, Cu12a-π can be transformed into cluster-based nonporous adaptive crystals (Cu12b-NACs) via ligand-exchange following a dissociation-reassembly mechanism. Moreover, Cu12a-π can efficiently remove 97.2% of iodine from saturated iodine aqueous solutions with a high uptake capacity of 2.96 g·g-1. These prospective results positioned at cluster-based porous supramolecular framework and enlighten follow-up researchers to design and synthesize such materials with better performance.

Dicarboxylic Acids Induced Tandem Transformation of Silver Nanocluster.

Structural transformation of metal nanoclusters (NCs) is of great ongoing interest regarding their synthesis, stability, and reactivity. Although sporadic examples of cluster transformations have been reported, neither the underlying transformation mechanism nor the intermediates are unambiguous. Herein, we have synthesized a flexible 54-nuclei silver cluster (Ag54) by combining soft (tBuC≡C-) and hard (nPrCOO-) ligands. The existence of weakly coordinated nPrCOO- enhances the reactivity of Ag54, thus facilitating the dicarboxylic acid to induce structural transformation. X-ray structural analyses reveal that Ag54 transforms to Ag28 cluster-based 2D networks (Ag28a and Ag28b) induced by H2suc (succinic acid) and H2glu (glutaric acid), whereas with H2pda (2,2'-(1,2-phenylene)diacetic acid), a discrete Ag28 cluster (Ag28c) is isolated. The key intermediate Ag17 that emerges during the self-dissociation of Ag54 was isolated by using cryogenic recrystallization and characterized by X-ray crystallography. The "tandem transformation" mechanism for the structure evolution from Ag54 to Ag28a is established by time-dependent electrospray ionization mass spectrometry (ESI-MS) and UV-vis spectroscopy. In addition, the catalytic activity in the 4-nitrophenol reduction follows the sequence Ag28c > Ag28b > Ag28a > Ag54 due to more bare silver sites on the surface of the Ag28 cluster unit. Our findings not only open new avenues to the synthesis of silver NCs but also shed light on a better understanding of the structural transformation mechanism from one cluster to another or cluster-based metal-organic networks induced by dicarboxylates.

Solvent-Mediated Separation and Reversible Transformation of 1D Supramolecular Polymorphs Built from [W10O32]4- Templated 48-Nuclei Silver(I) Cluster.

Although the C-H···O interaction is an essential component in determining the molecular packing in solids and the properties in supramolecular chemistry, it presents a significant challenge when trying to use it in the crystal engineering of complex metallosupramolecules, even though it is a relatively weak supramolecular force. The first pair of high-nuclearity silver-cluster-based one-dimensional (1D) polymorphs built from supramolecular synthon [W10O32@Ag48(CyS)24(NO3)16]·4NO3 (Cy = cyclohexyl) bridged by four grouped inorganic NO3- ligands is initially synthesized as a mixed phase and further individually crystallized as a pure phase by virtue of tuning intermolecular C-H···O interaction through altering the composition ratio of ternary solvent system. Increasing highly polar and hydrogen-bonding methanol strengthens the solvation effect reflected by the change of coordination orientation of surface NO3- ligands, which dominates the packing of the 1D chains in the crystal lattice, resulting in the crystallization of polymorphs from tetragonal to monoclinic. The two crystalline forms can also be reversibly transformed to each other in an appropriate solvent system. Correspondingly, the two polymorphs display distinct temperature-dependent photoluminescence behaviors, which are ascribed to the variation of noncovalent interchain C-H···O interactions along with the temperature. More importantly, benefiting from the suppression of fluorescence, both polymorphs offer excellent photothermal conversion properties which were further applied to remote-controlled laser ignition. These findings may open more avenues for the application of solvent-mediated intermolecular interaction in controlling the molecule arrangement as well as the optical properties.

Two triplet emitting states in one emitter: Near-infrared dual-phosphorescent Au20 nanocluster.

Intrinsic dual-emission (DE) of gold nanoclusters in the near-infrared (NIR) are fascinating for fundamental importance and practical applications, but their synthesis remains a formidable challenge and sophisticated excited-state processes make elucidating DE mechanisms much more arduous. Here, we report an all-alkynyl-protected gold nanocluster, Au20, showing a prolate Au12 tri-octahedral kernel surrounded by two Au2(CZ-PrA)3 dimers, four Au(CZ-PrA)2 monomers, and two CZ-PrA- bridges. Au20 exhibits distinguished photophysical properties including NIR DE at 820 and 940 nm, microsecond radiative relaxation, and 6.26% photoluminescent quantum yield at ambient environment in nondegassed solution. Combining systematic studies on steady/transient spectroscopy and theoretical calculation, we identified two triplet charge transfer (CT) states, ligand-to-kernel and kernel-based CT states as DE origins. Furthermore, this NIR DE exhibits highly independent and sensitive response to surrounding environments, which well coincide with its mechanism. This work not only provides a substantial structure model to understand a distinctive DE mechanism but also motivates the further development of NIR DE materials.

Regulating the assembly and expansion of the silver cluster from the Ag37 to Ag46 nanowheel driven by heteroanions.

Precise control over the shape and size of metal nanoclusters through anion template-driven self-assembly is one of the key scientific goals in the nanocluster community, however, it is still not understood comprehensively. In this work, we report the controllable synthesis and atomically precise structures of silver nanowheels Ag37 and Ag46, using homo (Cl- ions) and heteroanion (Cl- and CrO4 2- ions) template strategies, along with macrocyclic p-phenyl-thiacalix[4]arene and small iPrS- ligands. Structural analyses revealed that in Ag37, Cl- ions serve as both local and global templates, whereas CrO4 2- ions function as local and Cl- ions as global templates in Ag46, resulting in a pentagonal nanowheel (Ag37) and a hexagonal (Ag46) nanowheel. The larger ionic size and more negative charges of CrO4 2- ions than Cl- ions offer more coordination sites for the silver atoms and are believed to be the key factors that drive the nanowheel core to expand significantly. Also, by taking advantage of the deep cavity of thiacalix[4]arene with an extended phenyl group, Ag46 has been used as a host material for dye adsorption depending on the charge and size of organic dyes. The successful use of heteroanions to control the expansion of well-defined silver nanowheels fills the knowledge gap in understanding the directing role of heteroanions in dictating the shape and size of nanoclusters at the atomic level.

Acute hepatitis of unknown aetiology among children around the world.

By 26 August 2022, the number of cases of acute hepatitis of unknown etiology (AHUA) has drastically increased to 1115 distributed in 35 countries that fulfill the World Health Organization definition. Several hypotheses on the cause of AHUA have been proposed and are being investigated around the world. In the recent United Kingdom (UK) report, human adenovirus (HAdV) with adeno-associated virus (AAV) co-infection is the leading hypothesis. However, there is still limited evidence in establishing the causal relationship between AHUA and any potential aetiology. The leading aetiology continues to be HAdV infection. It is reported that HAdV genomics is not unusual among the population in the UK, especially among AUHA cases. Expanding the surveillance of HAdV and AAV in the population and the environment in the countries with AUHA cases is suggested to be the primary action. Metagenomics should be used in detecting other infectious pathogens on a larger scale, to supplement the detection of viruses in the blood, stool, and liver specimens from AUHA cases. It is useful to develop a consensus-specific case definition of AHUA to better understand the characteristics of these cases globally based on all the collected cases.

Bicarbonate insertion triggered self-assembly of chiral octa-gold nanoclusters into helical superstructures in the crystalline state.

Constructing atomically precise helical superstructures of high order is an extensively pursued subject for unique aesthetic features and underlying applications. However, the construction of cluster-based helixes of well-defined architectures comes with a huge challenge owing to their intrinsic complexity in geometric structures and synthetic processes. Herein, we report a pair of unique P- and M-single stranded helical superstructures spontaneously assembled from R- and S-Au8c individual nanoclusters, respectively, upon selecting chiral BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthalene) and hydrophilic o-H2MBA (o-mercaptobenzoic acid) as protective ligands to induce chirality and facilitate the formation of helixes. Structural analysis reveals that the chirality of the Au8c individual nanoclusters is derived from the homochiral ligands and the inherently chiral Au8 metallic kernel, which was further corroborated by experimental and computational investigations. More importantly, driven by the O-H⋯O interactions between (HCO3 -)2 dimers and achiral o-HMBA- ligands, R/S-Au8c individual nanoclusters can assemble into helical superstructures in a highly ordered crystal packing. Electrospray ionization (ESI) and collision-induced dissociation (CID) mass spectrometry of Au8c confirm the hydrogen-bonded dimer of Au8c individual nanoclusters in solution, illustrating that the insertion of (HCO3 -)2 dimers plays a crucial role in the assembly of helical superstructures in the crystalline state. This work not only demonstrates an effective strategy to construct cluster-based helical superstructures at the atomic level, but also provides visual and reliable experimental evidence for understanding the formation mechanism of helical superstructures.

Sulfide Boosting Near-Unity Photoluminescence Quantum Yield of Silver Nanocluster.

Silver nanoclusters have emerged as promising candidates for optoelectronic applications, but their room-temperature photoluminescence quantum yield (PLQY) is far from ideal to access cutting-edge device performance. Herein, two supertetrahedral silver nanoclusters with high PLQY in non-degassed solution at room temperature were constructed by interiorly supporting the core with multiple VO43- and E2- anions as structure-directing agents and exteriorly protecting the core with a rigid ligand shell of PhC≡C- and Ph2PE2- (E = S, Ag64-S; E = Se, Ag64-Se). Both clusters have similar outer Ag58 tetrahedral cages and [Ag6E4@(VO4)4] cores, forming a pair of comparable clusters to decrypt the origin of such a high PLQY, particularly in Ag64-S, where the PLQY reached up to 97%. The stronger suppression effect of inner sulfides for nonradiative decay is critical to boost the PLQY to near unity. Transient absorption spectroscopy is employed to confirm the phosphorescence nature. The quadruple-capping assembly mechanism involving Ag7 secondary building units on a Ag36 truncated tetrahedron was also established by collision-induced dissociation studies. This work not only provides a strategy of core engineering for the controlled syntheses of silver nanoclusters with high PLQY but also deciphers the origin of a near-unity PLQY, which lays a foundation for fabricating highly phosphorescent silver nanoclusters in the future.

Solvent-Induced Isomeric Cu13 Nanoclusters: Chlorine to Copper Charge Transfer Boosting Molecular Oxygen Activation in Sulfide Selective Oxidation.

Isomers with minimal structural dissimilarities are promising research objects to obtain a comprehensive understanding of structure-property relationships; however, comparability of isomeric structures is a prerequisite. Herein, two quasi-structurally isomeric 13-nuclei copper nanoclusters (Cu NCs) (Cu13a and Cu13b) containing highly similar Cu13 kernels and different arrangements of peripheral ligands were obtained using a solvent-induced strategy. The exotic chloride ion is shown to play a prominent role in inducing the selective formation of two quasi-isomers, where the comparative study to establish a structure-property relationship was realized. Due to the charge transition from chlorine to the copper core (X(Cl)M(Cu)CT), the molecular oxygen activation of Cu13a showed higher singlet oxygen (1O2) and lower superoxide radical (O2•-) yields compared to those of Cu13b, which gives it better catalytic selectivity for the 1O2 involved selective oxidation of sulfides. The present work not only offers a controllable strategy for the rational design and synthesis of quasi-structurally isomeric Cu NCs but also provides a pathway to boost catalytic selectivity by a halogen to metal core charge transition.

Nuclearity enlargement from [PW9O34@Ag51] to [(PW9O34)2@Ag72] and 2D and 3D network formation driven by bipyridines.

The structural transformations of metal nanoclusters are typically quite complex processes involving the formation and breakage of several bonds, and thus are challenging to study. Herein, we report a case where two lacunary Keggin polyoxometallate templated silver single-pods [PW9O34@Ag51] (SD/Ag51b) fuse to a double-pod [(PW9O34)2@Ag72] by reacting with 4,4'-bipyridine (bipy) or 1,4-bis(4-pyridinylmethyl)piperazine (pi-bipy). Their crystal structures reveal the formation of a 2D 44-sql layer (SD/Ag72a) with bipy and a 3D pcu framework (SD/Ag72c) with pi-bipy. The PW9O349- retains its structure during the cluster fusion and cluster-based network formation. Although the two processes, stripping of an Ag-ligands interface followed by fusion, and polymerization, are difficult to envisage, electrospray ionization mass spectrometry provides enough evidences for such a proposal to be made. Through this example, we expect the structural transformation to become a powerful method for synthesizing silver nanoclusters and their infinite networks, and to evolve from trial-and-error to rational.

Solvent-Controlled Condensation of [Mo2 O5 (PTC4A)2 ]6- Metalloligand in Stepwise Assembly of Hexagonal and Rectangular Ag18 Nanoclusters.

Stepwise assembly starting from a preassembled metalloligand is a promising approach to obtain otherwise unattainable silver nanoclusters, but hard to be intrinsically identified due to the lack of convincing evidence to justify such a process. Herein, hexagonal and rectangular Ag18 nanoclusters are constructed from the [Mo2 O5 (PTC4A)2 ]6- (H4 PTC4A=p-phenyl-thiacalix[4]arene) metalloligand through stepwise assembly. The formation of the metalloligand is confirmed by electrospray ionization mass spectrometry, then assembled with silver ions to form two geometrically different Ag18 nanoclusters in different solvents. The cyclization from the metalloligand to [(Mo2 O5 PTC4A)6 ]12- can be realized without alcohols and otherwise blocked by them. The installation of this metalloligand not only provides comprehensive understanding of how the solvents regulate the silver nanocluster structures, but also brings new insights for the controllable ligand metallization and subsequent condensation.

Real-Time Fluorescent Monitoring of Kinetically Controlled Supramolecular Self-Assembly of Atom-Precise Cu8 Nanocluster.

Kinetically stable and long-lived intermediates are crucial in monitoring the progress and understanding of supramolecular self-assembly of diverse aggregated structures with collective functions. Herein, the complex dynamics of an atomically precise CuI nanocluster [Cu8 (t BuC6 H4 S)8 (PPh3 )4 ] (Cu8a) is systematically investigated. Remarkably, by monitoring the aggregation-induced emission (AIE) and electron microscopy of the kinetically stable intermediates in real time, the directed self-assembly (DSA) process of Cu8a is deduced. The polymorphism and different emission properties of Cu NCs aggregates were successfully captured, allowing the structure-optical property relationship to be established. More importantly, the utilization of a mathematical "permutation and combination" ideology by introducing a heterogeneous luminescent agent of a carbon dot (CD) to Cu8a aggregates enriches the "visualization" fluorescence window, which offers great potential in real time application for optical sensing of materials.

Thermally Hypsochromic or Bathochromic Emissions? The Silver Nuclei Does Matter.

Structural modulation of core-shell silver nanoclusters from the inside is a huge challenge but of great importance in their syntheses. Herein, two silver nanoclusters [Ag3 S9 @Ag42 ] (SD/Ag45b) and [Ag9 S9 @Ag42 ] (SD/Ag51a) are isolated in the presence of different kinds of sulfonic acids. Uniquely, SD/Ag45b and SD/Ag51a show typical core-shell structures with the similar Ag42 shell but different cores. The outer shell of 42 silver atoms comprises two Ag3 trigons at two poles encircled by three equatorial distorted square cupolas (J4 , Ag12 ). The core in SD/Ag45b is a silver trigon ligated by nine S2- ions (Ag3 S9 ), while a tricapped triangular prismatic Ag9 also ligated by the same amount of S2- ions (Ag9 S9 ) is observed in the inner core of SD/Ag51a. The electrospray ionization mass spectrometry (ESI-MS) indicates that the introduction of p-toluenesulfonic acid can realize the transformation from SD/Ag45b to Ag51 . SD/Ag45b and SD/Ag51a show inverse luminescence thermochromic behaviors in the near-infrared (NIR) region, mainly dictated by the inner silver cores. This work not only realizes the synthesis of new silver nanoclusters by core modulation but also provides a prototype to get molecular-level insight into the correlation between structure and luminescence thermochromism.

Structural rearrangement of Ag60 nanocluster endowing different luminescence performances.

It is well known that structure determines property, but obtaining a pair of silver nanoclusters with comparable structures to understand the structure-property relationship is a very challenging task. A new 60-nuclei silver nanocluster (SD/Ag60a) protected by a mixed-ligand shell of tBuS- and o-CH3OPhCOO- was obtained and characterized. Single crystal x-ray diffraction reveals that SD/Ag60a has an identical metal nuclearity and core-shell structural type to SD/Ag1 previously reported by our group, whereas the compositions of the core and shell have undergone a rearrangement from an Ag12 cuboctahedron core and an Ag48 rhombicuboctahedron shell in SD/Ag1 to an Ag14 rhombic dodecahedron core and an oval Ag46 shell in SD/Ag60a. The core enlargement from Ag12 to Ag14 originates from the replacement of two S2- in Ag12S15 by two Ag+, which gives a new Ag14S13 core. This result indicates that the metal frameworks of silver nanoclusters have some extent flexibility despite the same nuclearity, which can be influenced by ligands, solvents, anion templates, and others in the embryonic stage of the assembly. Interestingly, different core-shell architectures of Ag60 nanoclusters also significantly endow the different optical absorption bands, photocurrent-generating properties, and luminesecent behaviors. This work not only realizes the regulation of the core-shell structure of silver nanoclusters with the same nuclearity but also provides a comparable model for investigating the relationship of structure-photoelectric properties.

A Carbonate-Templated Decanuclear Mn Nanocage with Two Different Silsesquioxane Ligands.

The mild reaction of the preorganized silsesquioxane precursor with Mn(II) acetate under ambient conditions results in a mixed-valent {MnII6MnIII4} nanocage (SD/Mn10) which is protected by both acyclic trimer [Si3] and cyclic tetramer [Si4]. Serendipitous capture of atmospheric CO2 as a µ5-carbonate anion placed at the center supports the formation of the cluster. The magnetic analysis reveals the strong antiferromagnetic interactions between Mn ions. Moreover, the drop-casting film of SD/Mn10 shows photoelectric activity indicating its great potential as a semiconductor for photoelectric conversion applications.

Toward Controlled Syntheses of Diphosphine-Protected Homochiral Gold Nanoclusters through Precursor Engineering.

Controllable syntheses of Au nanoclusters (NCs) with different nuclearities are of great significance due to the kernel-dependent physicochemical properties. Herein, two pairs of enantiomeric Au NCs [Au19(R/S-BINAP)4(PhC≡C)Cl4] (SD/Au19) and [Au11(R/S-BINAP)4(PhC≡C)2]·Cl (SD/Au11), both with atropos (rigid axial chirality) diphosphine BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthalene) as the predominant organic ligands, were controllably synthesized through precursor engineering. The former was obtained by direct reduction of HAuCl4·4H2O, while the latter was obtained by reduction of [Au(SMe2)Cl] instead. Intriguingly, the kernel of SD/Au19 contains an Au7 pentagonal bipyramid capped by two boat-like Au6 rings, which represents another type of Au19 kernel, making SD/Au19 a good candidate for comparative study with other Au19 NCs to get more insight into the distinct structural evolution of phosphine-protected Au NCs. Despite the previous chiroptical studies on some other chiral undecagold NCs, the successful attainment of the X-ray crystal structures for SD/Au11 not only provides a step forward toward better correlating the chiroptical activities with their structural details but also reveals that even the auxiliary protecting ligands also play a nontrivial role in tuning the geometrical structures of the metal NCs. The chiroptical activities of both SD/Au19 and SD/Au11 were found to originate from the chiral ligands and core distortions; the extended π-electron systems in the BINAP ligands have proved to positively contribute to the electronic absorptions and thus disturb the corresponding circular dichroism (CD) responses.