Controlled modulation of the specific crystal surfaces is vital in nanotechnology but remains challenging to implement. Here, we achieve sequential vertex modulation in atomically precise homochiral silver nanoclusters using a scalable crystallization synthesis. By tuning the reductant conditions, we generate mixed-phase cocrystallized R/S-Ag19·Ag20 comprising enantiopure R/S-Ag19 and R/S-Ag20, featuring the first icosahedral Ag13 core with 6 electrons. Using kinetic and thermodynamic control, we sequentially add Ag atoms to the cubic facets, progressing from the Ag6 shell in R/S-Ag19 (two missing vertices) to the Ag7 shell in R/S-Ag20 (one missing vertex), and ultimately to the closed Ag8 shell in R/S-Ag21, and luminescence is induced. This geometric evolution is reminiscent of the arachno → nido → closo transformations in borane clusters, where vertex recovery leads to increasingly close polyhedral frameworks. Shell closure results in 2e filling, symmetry adaptation and chirality mutation. Additionally, R/S-Ag21 enables quantitative chiral sensing of amino acids. This work advances nanosynthesis by providing a framework for controlling surface modulation and fine-tuning the nanocluster properties and can be used to facilitate the development of improved functional (chiral) nanomaterials.

To address the limited understanding of how the Pb2+ coordination geometry governs photoluminescence (PL) in low-dimensional lead halides, we employ halogen bonding (XB) as a strategic tool to systematically modify one-dimensional (1D) hybrid perovskite structures. By varying the halide composition and incorporating XB donors, single-crystal diffraction and density functional theory (DFT) calculations uncover a fundamental restructuring of the coordination environment. The iodoplumbate-based system without XB forms a conventional octahedral geometry, whereas its chloroplumbate analogue adopts an asymmetric "5 + 1" arrangement. Introducing XB dramatically reshapes both, driving them toward a previously unreported "5 + 2" pseudo-seven-coordinate structure, where an added Pb···X-C interaction imposes significant lattice distortion. Low-temperature (77 K) PL resolves distinct emission bands near 500 and 600 nm, assigned to free exciton (FE) and self-trapped exciton (STE) emission, respectively. Crucially, XB-modified iodoplumbate exhibits a pronounced enhancement of the STE emission alongside a subtle suppression of the FE band, whereas the chloride analogue lacks this prominent long-wavelength feature. This contrast underscores the role of the specific "5 + 2" coordination, which fosters carrier localization and stabilizes STE formation. This work demonstrates that precise coordination control via XB is a powerful method for enhancing structural complexity and deliberately tuning optoelectronic performance in low-dimensional perovskite materials.

A simple crystalline material system (1,8-octanediammonium dihalides, ODAHX, X = Cl, Br, I) is capable of dynamically capturing molecular iodine through unique "adaptive hydrogen-bonded networks (HBNs)." The system achieves an exceptional I-2 uptake capacity up to 8.0 molmol(-1) (ODAHI) with >95% efficiency after 5 cycles, while time-dependent X-ray diffraction characterization identifies as many as four distinct intermediate phases for ODAHCl during iodine incorporation. Combining crystallographic analysis, adsorption kinetics, and DFT calculations, we reveal how multiple halogen-bonded motifs between halide and I-2 molecules, conformational flexibility of the organic cation, and tunable NHX- hydrogen bonds enable continuous structural evolution during iodine adsorption. Notably, X-I-2 halogen bonding initiates the adsorption and further drives the penetration of I-2 molecules, along with the synergistic adjustment of the HBNs and adaptive change of the ODAH(2+) conformations. This work provides atomic-level evidence for spontaneous void-gas creation in originally nonporous networks and thus redefines the engineering principles for next-generation smart adsorbents targeting pollutant molecules.

Constructing luminescent metal clusters templated by the acetylide dianion (C22−) and developing N-heterocyclic carbene (NHC)-stabilized clusters are both highly attractive; however, integrating these two motifs within a single platform remains a formidable challenge. Here, we report a mild, room-temperature strategy for controlled in situ release of C22− from NHCAuCCH precursors in a dichloromethane/methanol medium. This method yields two unprecedented C22−-linked trinuclear gold clusters (Au3-1 and Au3-2) and, upon copper incorporation, two tetranuclear heterometallic clusters (Au2Cu2 and Au2Cu2·Et2O). Despite identical monomeric building blocks, Au3-1 and Au3-2 exhibit distinct crystal packings, resulting in markedly different solid-state photophysics: both show temperature- and excitation-dependent dual phosphorescence. In contrast, the Au2Cu2 exhibit excitation-independent single emission. Beyond clarifying the roles of packing and metal composition in determining the multiplicity of emissive states, the excitation-gated color outputs of these solution-processable phosphorescent clusters enable wavelength-selective decoding for multilevel optical security. These findings demonstrate the utility of C22− templating as a versatile synthetic strategy, offer fundamental insights into the structure–property relationships of carbene-stabilized phosphorescent metal clusters, and provide design guidelines for programmable photonic materials.

High-temperature oxidation reactions catalyzed by earth-abundant transition metal oxides are vital for numerous industrial and environmental processes. However, their performance is often limited by the rapid desorption of active oxygen species at high temperatures. Here, we describe a straightforward approach to constructing a CuMn spinel/Mn2O3 composite oxide catalyst that addresses this limitation and demonstrate that lattice oxygen can spontaneously migrate to form interface-stabilized superoxo species under high-temperature reaction conditions. This catalyst exhibits a 14-fold enhancement in the CH4 oxidation reaction compared to Mn2O3, with activity and stability even better than those of many reported noble-metal supported catalysts. In situ characterizations and theoretical calculations reveal that the superoxo species accept electrons from the neighboring Cu and Mn atoms, exhibiting enhanced ability for C-H activation. This work illustrates the critical role of interface-stabilized superoxo species in CH4 oxidation and establishes a promising route for promoting high-temperature catalytic processes through interface engineering.

The formation of core-shell metal nanoclusters (NCs) with high symmetry remains significantly challenging. Here, we report the first synthesis and atomically precise structures of two discoidal clusters, Ag69 and Ag78, protected by mixed thiol ligands, both exhibiting rare pseudo-6-fold symmetry, with crystallographic disorder considered. While their sizes and skeletons are similar, the key difference arises from the introduction of Cl- ions from in situ decomposition of CH2Cl2 in the assembly of Ag69. Replacing Cl-, S2- ions occupy the same positions in Ag78, leading to stronger silver-sulfur coordination and closer silver-silver distances. Notably, within the crystal lattice of Ag69, an additional Ag78 forms at the same location. Ag69 and Ag68 share an identical outer shell of Ag54S6(tBuS)24(tBuPhS)24, but differ at the core, with Ag69 having Ag15Cl6(tBuPhS)2 and Ag68 having Ag14Cl6(tBuS)2. We also discuss the photoluminescent properties, and the photocatalytic degradation of organic dyes is also discussed. This work provides valuable insights into the formation of high-symmetry metal NCs and their potential applications in photochemistry.

Ruthenium(III) complexes are promising anticancer metallodrugs because of their antimetastatic (migrastatic) potential and significantly lower host toxicity than generally used platinum metallodrugs. On the other hand, the ruthenium(III) complexes generally show low solubility and stability in an aqueous environment but exhibit some toxicity associated with unspecific delivery. For these reasons, numerous ongoing studies deal with their encapsulation into various delivery systems to maximize their therapeutic efficacy. One of these systems can also be crystals of nontoxic metal-organic frameworks (MOFs). In this work, we studied incorporation of a bioactive ruthenium(III) complex (RuC) inside MOFs derived from γ-cyclodextrin (γ-CD) and biocompatible potassium ions, forming CD-MOF-1. Viability studies in vitro were carried out using spheroids of human hepatoblastoma cell line HepG2. These studies revealed that the RuC-CD-MOF-1 system provides effective cancer cell suppression through slow gradual release over a longer period (>10 days) while reducing acute cytotoxic effects associated with naked RuC. This combination was defined for further development and optimization as a drug-delivery platform for metallodrugs.

Deprotonation of the Schiff base 2,6-dimethyl- N -(1-phenylethylidene)aniline, C 16 H 17 N or [MeC(Ph)=N(2,6-Me 2 C 6 H 3 )], 1 , with one equivalent of lithium diisopropylamide (LDA) and subsequent reaction with half an equivalent of SiPh 2 Cl 2 gave a new diimine, N -[2-({2-[(2,6-dimethylphenyl)imino]-2-phenylethyl}diphenylsilyl)-1-phenylethylidene]-2,6-dimethylaniline, C 44 H 42 N 2 Si, 2 . Further treatment of 2 with LDA in the presence of tetrahydrofuran (THF) yielded the target binuclear ansa -bis(1-azaallyl) lithium compound {μ- N -[2-({2-[(2,6-dimethylphenyl)azanidyl]-2-phenylethyl}diphenylsilyl)-1-phenylethylidene]-2,6-dimethylanilinido}bis[(tetrahydrofuran)lithium], [Li 2 (C 44 H 40 N 2 Si)(C 4 H 8 O) 2 ], 3 . Both 2 and 3 were characterized by 1 H and 13 C NMR spectroscopy and elemental analysis, and the structures of 1 , 2 and 3 were confirmed by X-ray crystallography. Density functional theory (DFT) calculations were carried out for compounds 1 – 3 . In addition, the catalytic properties of 3 towards the ring-opening polymerization of ɛ-caprolactone were investigated and the compound showed good catalytic activity.

Catalytic asymmetric dearomatization reactions of alpha-unsubstituted beta-naphthols are very challenging due to the high energy barrier resulting from the loss of aromaticity. Herein, we describe an example of enantioselective catalytic dearomative spiroannulation with yne-allylic esters. The success of this reaction relied on the copper-catalyzed remote asymmetric strategy using yne-allylic esters as the bis-electrophilic reagents. This transformation features mild reaction conditions, broad functional group tolerance, and an extensive substrate scope, thereby facilitating the efficient construction of an array of enantioenriched naphthalene-2-one and spiroindolenine derivatives. Experimental studies and density functional theory calculations establish the reaction pathway and origin of stereoselectivity.

Materials exhibiting X-ray-induced photochromism have consistently piqued the interest of researchers. Exploring the photochromic properties of such materials is valuable for understanding the structural changes and electron transfer processes that occur under high energy radiation, such as X-ray irradiation. Here, a crystalline silver(I) nanocluster synthesized from tert-butylacetylene silver was found to have the ability to exhibit color and photoluminescence changes upon exposure to X-ray radiation. The responsive behavior was observed across a wide temperature range of 100-300 K, with the ability to respond particularly well to soft X-rays (λ > 1 Å) and exhibit light responsiveness to hard X-rays (λ < 1 Å). By combining experimental findings including X-ray diffraction, X-ray photoelectron spectroscopy, electron spin resonance, etc. with theoretical calculations, we have proposed that X-ray irradiation induces electron transfer from chloride (Cl-) located in the center of the silver(I) nanocluster to the surrounding Ag14 in the skeleton. This represents the first documented example in which electron transfer induced by X-ray excitation has been observed, accompanied by a photochromism process, in silver nanoclusters. This study contributes to our understanding of X-ray-induced photochromism and the electron transfer process in silver cluster compounds. It also provides valuable insights and potential design strategies for applications such as photochromism, photoluminescence color change, and photoenergy conversion.

Coinage metal (Au, Ag, Cu) cluster and polyoxometalate (POM) cluster represent two types of subnanometer "artificial atoms" with significant potential in catalysis, sensing, and nanomedicine. While composite clusters combining Ag/Cu clusters with POM have achieved considerable success, the assembly of gold clusters with POM is still lagging. Herein, we first designedly synthesized two cluster structural units: an Au3O cluster stabilized by diverse N-heterocyclic carbene (NHC) ligands and an amine-terminated POM linker. The subsequent reaction involved amine substitution in the POM linker for the central O atom in the Au3O cluster, resulting in the first ternary composite cluster-a POM cluster sandwiched by two Au clusters protected by NHCs. Single-crystal X-ray diffraction and other characteristic methods characterized their atomically precise structures. Furthermore, altering the NHC ligands decreased the number of gold atoms in the sandwich structures, accompanying the different protonated degrees of amine ligand in the terminal end of the POM linker. These composite clusters showed excellent performances in catalytic H2O2 conversion through the synergistic effect between gold clusters and POM clusters. This work opens a new avenue to functional composite metal clusters and would promote their enhanced catalysis applications through intercluster synergistic interactions within composite systems.

Central metal exchange can innovatively open the cavity of metal-organic frameworks (MOFs) by alternating the framework topology. Here, the single-crystal-to-single-crystal (SC-SC) transformation is reported from a Co-based MOF {[Co1.25 (HL)0.5 (Pz-NH2 )0.25 (µ3 -O)0.25 (µ2 -OH)0.25 (H2 O)]·0.125 Co·0.125 L·10.25H2 O}n (Co-MOF, L = 5,5'-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid) into two novel MOF materials, {[Cu1.75 L0.75 (Pz-NH2 )0.125 (µ3 -O)0.125 (µ2 -OH)0.25 (H2 O)0.375 ]•3CH3 CN}n (Cu-MOF) and {[Zn1.75 L0.625 (Pz-NH2 )0.25 (µ3 -O)0.25 (µ2 -O)0.25 (H2 O)1.25 ]•4CH3 CN}n (Zn-MOF), through exchanging the Co2+ in the MOF into Cu2+ or Zn2+ , respectively. The free Co2+ and L4- in the Co-MOF channels fuse with the skeleton during the Co→Cu and Co→Zn exchange processes, leading to the expansion of the channel space and the transformation of the secondary building units (SBUs) to form an adjustable skeleton. The nonlinear optical response results show that the MOFs generated by the exchange of the central metal exhibit different saturable absorption and the self-focusing effect. In addition, loading polypyrrole (PPy) into the MOFs can not only improve the stability of the MOFs but also further optimize the nonlinear optical behavior. This work suggests that SC-SC central metal exchange and the introduction of polymer molecules can tune the nonlinear optical response, which provides a new perspective for the future study of nonlinear optical materials.

Surface lattice oxygen (O-latt) over transition metal oxides plays a pivotal role in catalytic combustion of automobile exhaust. The insufficient O-latt activity at low temperatures, however, remains the key problem restricting its practical application. To overcome this deficiency, we activated the Olatt of mullite SmMn2O5 through the interface fabrication with spinel Co3O4. The optimized Co3O4/SmMn2O5 catalyst exhibited 90% conversion at 247 ? for the typical automobile exhaust propane combustion, 77 ? lower than the original SmMn2O5. Additionally, Co3O4/SmMn2O5 showed extremely high stability even under harsh operating temperature (e.g., 800 ?). Experimental and theoretical calculation results revealed that the regulated interface of Co3O4/SmMn2O5 facilitated the electrons transfer from SmMn2O5 to Co3O4, contributing to the enhanced propane adsorption and catalytic oxidation activity due to the formation of electrophilic oxygen in SmMn2O5 around the interface. This work can provide a basic understanding of the Olatt activation for developing efficient automobile exhaust combustion catalysts.

Metal-organic frameworks (MOFs) have aroused ever-growing scientific interest for photocatalytic CO2 reduction reaction (CO2RR). Delicate design and synthesis of MOFs with open metal sites (OMSs) is the key to activate CO2 and even stabilize the reaction intermediates of CO2RR, further determine the superior selectivity. Herein, two amino-functionalized MOFs (Ni-Bpyb and Ni-Bipy) with open Ni(II) sites were constructed from 2 '-amino-5 '-(4-carboxyphenyl)-[1,1 ':3 ',1 ''-terphenyl]-4,4 ''-dicarboxylic acid (NH2-BTBH3) and different lengths of linear N -donor linkers, 1,4-bis(4-pyridyl) benzene (Bpyb) or 4,4 '-bipyridine (Bipy). Under visible-light irradiation, Ni-Bpyb shows more excellent CO yield of 1326.7 mu mol center dot g(-1)center dot h(-1) with impressive apparent quantum efficiency (AQE, 2.12 %@420 nm) and selectivity (98.80 %). Significantly, this AQE value is at the high end among MOFs-based photocatalysts for CO2RR. The reaction mechanism has been carefully investigated by experimental and theo-retical calculations results. Photoelectric experiments demonstrate that Ni-Bpyb shows higher electron-hole separation efficiency compared to Ni-Bipy. Theoretical calculations validate that the open Ni(II) sites of Ni-Bpyb possess lower energy barriers of CO2 adsorption and reducing CO2* to COOH*, as well as better stabilizes COOH* intermediate than those of Ni-Bipy. These merits synergistically contribute to the superior performance and selectivity of Ni-Bpyb. This work might give a guidance for the design of efficient MOFs-based photocatalysts with excellent selectivity for CO2RR.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Circularly polarized luminescence (CPL) materials have attracted considerable attention for their promising applications in encryption, chiral sensing, and three-dimensional (3D) displays. However, the preparation of high-efficiency, pure blue CPL materials remains challenging. In this study, we reported an enantiomeric pair of triangle copper(I) clusters (R/S-Cu3) rigidified by employing chiral N-heterocyclic carbene (NHC) ligands with two pyridine-functionalized wingtips. These chiral clusters emitted pure blue phosphorescence that overlapped with that of the commercial blue phosphor having Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of (0.14, 0.10), and the films exhibited an unprecedented photoluminescence quantum yield (PLQY) of ∼70.0%. Additionally, the solutions showed very bright circularly polarized phosphorescence (CPP) with a dissymmetry factor of ±2.1 × 10-3. The excellent solubility and photostability endowed these pure-blue-emitting chiral clusters with promising applications as pure blue CPP inks for 3D printing white objects, such as precise-atomic-enlarged models of metal clusters and a lovely white stereoscopic "rabbit". The intricate mechanism underlying blue phosphorescence in this small cluster and across various states is elucidated through a comprehensive approach that integrates thorough analysis of luminescence properties, controlled experiments, and theoretical calculations. For the first time, we propose that the dominant high-energy emission center is constituted by delocalized hybrid orbitals over multiple atomic centers, encompassing both the metal and the coordinated atoms. This challenges stereotypical assumptions that the cluster center solely supports low-energy emissions. This work expands the currently limited range of CPP functional materials and provides a new direction for CPP applications involving NHC-stabilized metal clusters.

Successive structural transformations were observed in a methanolic solution containing 4-iodo-1-methylpyridin-1-ium iodide (IPyMe·I) and bismuth iodide (BiI3). When kept in the solution, the amorphous solid (P_1) obtained immediately on mixing would transform to needle crystals (C_1) in hours, which would convert to prismatic crystals (C_2) in around 2 days. In the presence of hydroiodic acid, the hydrothermal reaction of IPyMe·I and BiI3 also gave rise to C_2, and crystals of C_2 in this solution would transform to a third crystalline product C_3 in ca. 3 days. X-ray single crystal diffraction experiments show C_1 containing one-dimensional {BiI4-}n chains, C_2 as a binuclear Bi2I93- structure, and C_3 consisting of a monomeric BiI63- unit, all with IPyMe+ as counter cations. Halogen bonds exist between IPyMe+ and the iodobismuthate, which may play key roles in the structural transformation. By introducing halogen bonding, the hybrids demonstrate excellent water-resistance. A thermal-induced reversible colour change from yellow to dark red occurred from 100 K to 450 K for all three hybrids, in which lattice expansion over the temperature range may be a reason for the thermochromism. The bandgaps derived from the UV-vis diffusion reflectance for the three complexes were 1.80 eV for C_1, 1.84 eV for C_2 and 2.00 eV for C_3. DTF computations followed by electron density topological analysis were applied to explain the structure-optical property relationship for complexes of diverse iodobismuthate types but the same counter cation. It was found that the nature of the Bi-I bonds rather than the dimensionality of the inorganic iodobismuthates is mainly responsible for the light absorption of the materials.

Water-soluble metallo-supramolecular cages with well-defined nanosized cavities have a wide range of functions and applications. Herein, we design and synthesize two series of metallo-supramolecular octahedral cages based on the self-assembly of two congeneric truxene-derived tripyridyl ligands modified with two polyethylene glycol (PEG) chains, i.e., monodispersed tetraethylene glycol (TEG) and polydispersed PEG-1000, with four divalent transition metals (i.e., Pd, Cu, Ni, and Zn). The resulting monodispersed cages C1-C4 are fully characterized by electrospray ionization mass spectrometry (ESI-MS), nuclear magnetic resonance (NMR) spectroscopy, and single-crystal X-ray diffraction. The polydispersed cages C5-C8 display good water solubilities and can act as nanoreactors to mediate visible-light-promoted C(sp3)-C(sp2) cross-dehydrogenative coupling reactions in an aqueous phase. In particular, the most robust Pd(II)-linked water-soluble polydispersed nanoreactor C5 is characterized by ESI-MS and capable of mediating the reactions with the highest efficiencies. Detailed host-guest binding studies in conjunction with control studies suggest that these cages could encapsulate the substrates simultaneously inside its hydrophobic cavity while interacting with the photosensitizer (i.e., eosin Y).

Luminescence is one of the most important properties for metal nanoclusters; however, clearly revealing its origin remains challenging. The different luminescence properties of the two prototypical 8e nanoclusters Au 11 and Au 13 remain elusive—Au 11 is always nonluminescent, whereas Au 13 is luminescent. In this work, by using a designed unique aromatic ligand (quinoline-2-thiol), we obtained new atomically precise phosphine-thiolate-protected neutral Au 11 - SH and cationic Au 13 - SH . In comparison with the classic phosphine-halide-protected Au 11 - Cl and Au 13 - Cl , the Cl-to-thiol alteration triggered room-temperature luminescence of the Au 11 core and dramatically modulated that of the Au 13 core. Ultrafast ultraviolet/infrared (UV/IR) spectroscopy, which is sensitive to organic aromatic groups, together with ultrafast transient absorption (TA) spectroscopy unprecedently revealed a relaxation process from the ligand to core state affecting the dynamics in excited states and some critical intermediate states favouring efficient room-temperature emission of these nanoclusters. This work provides some new insights into the origin of photoluminescence of metal nanoclusters and opens an avenue to modulate the dynamics of their excited states using aromatic ligands, which would have direct applications in lighting, light harvesting, and photocatalysis.

The origins of the chiroptical activities of inorganic nanostructures have perplexed scientists, and deracemization of high-nuclearity metal nanoclusters (NCs) remains challenging. Here, we report a single-crystal structure of Rac-Ag70 that contains enantiomeric pairs of 70-nuclearity silver clusters with 20 free valence electrons (Ag70), and each of these clusters is a doubly truncated tetrahedron with pseudo-T symmetry. A deracemization method using a chiral metal precursor not only stabilizes Ag70 in solution but also enables monitoring of the gradual enlargement of the electronic circular dichroism (CD) responses and anisotropy factor gabs. The chiral crystals of R/S-Ag70 in space group P21 containing a pseudo-T-symmetric enantiomeric NC show significant kernel-based and shell-based CD responses. The small symmetry breaking of Td symmetry arising from local distortion of Ag-S motifs and rotation of the apical Ag3 trigons results in large chiroptical responses. This work opens an avenue to construct chiral medium/large-sized NCs and nanoparticles, which are promising for asymmetric catalysis, nonlinear optics, chiral sensing, and biomedicine.