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 Cu 13 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 ( 1 O 2 ) and lower superoxide radical (O 2•− ) yields compared to those of Cu13b, which gives it better catalytic selectivity for the 1 O 2 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.

Controllable syntheses of Au nanoclusters (NCs) with different nuclearities are of great significance due to the kerneldependent physicochemical properties. Herein, two pairs of enantiomeric Au NCs [Au 19 (R/S-BINAP) 4 (PhCC)Cl 4 ] (SD/Au19) and [Au 11 (R/S-BINAP) 4 (PhCC) 2 ]•Cl (SD/Au11), both with atropos ( r i g i d a x i a l c h i r a l i t y ) d i p h o s p h i n e B I N A P ( 2 , 2 ′ -b i s -(diphenylphosphino)-1,1′-binaphthalene) as the predominant organic ligands, were controllably synthesized through precursor engineering. The former was obtained by direct reduction of HAuCl 4 •4H 2 O, while the latter was obtained by reduction of [Au(SMe 2 )Cl] instead. Intriguingly, the kernel of SD/Au19 contains an Au 7 pentagonal bipyramid capped by two boat-like Au 6 rings, which represents another type of Au 19 kernel, making SD/Au19 a good candidate for comparative study with other Au 19 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.

The low efficiency triplet emission of hybrid copper(I) iodide clusters is a critical obstacle to their further practical optoelectronic application. Herein, we present an efficient hybrid copper(I) iodide cluster emitter (DBA)4Cu4I4, where the cooperation of excited state structure reorganization and the metallophilicity interaction enables ultra‐bright triplet yellow‐orange emission with a photoluminescence quantum yield over 94.9 %, and the phonon‐assisted de‐trapping process of exciton induces the negative thermal quenching effect at 80–300 K. We also investigate the potential of this emitter for X‐ray imaging. The (DBA)4Cu4I4 wafer demonstrates a light yield higher than 104 photons MeV−1 and a high spatial resolution of ≈5.0 lp mm−1, showing great potential in practical X‐ray imaging applications. Our new copper(I) iodide cluster emitter can serve as a model for investigating the thermodynamic mechanism of photoluminescence in hybrid copper(I) halide phosphorescence materials.

The Keggin structure, known as an archetypical polyoxometalate (POM) structural motif, has widened up our fundamental understanding of the growth behavior of natural metal oxide minerals. However, devising a strategy for synthesis of such species consisting of pure-metal ions remains a great challenge. Different from those sixcoordinated early transition metal ions in Keggin POMs, lanthanide prefers higher coordination numbers, making the construction of lanthanide-Keggin structure more difficult. Here, we report the unprecedented luminescent Keggin-type Eu 13 nanocluster constructed through a facile solvothermal method using the high-symmetry macrocyclic tetrasilane (Ph 4 Si 4 O 8 ) 4− as the capping ligand. This protocol demonstrates an important proof of concept for assembly of metallasilsesquioxanes. The structure shows a rare polyoxometalate-Eu-oxo-core@SiO 2 -shell@organicshell (Eu13) consisting of a central EuO 8 cube, surrounded by 12 edge-sharing EuO 7 monocapped trigonal prisms. It is the highestnuclearity lanthanide−silsesquioxane nanocluster. Electrospray ionization mass spectrometry reveals that Eu13 is stable in solution except for some labile terminal dimethylformamide on the ligand shell, which endows Eu13 with a high catalytic activity for CO 2 cycloaddition reaction with small epoxides under ambient conditions. Eu13 also exhibits intense red luminescence upon visible light excitation (466 and 535 nm). The photophysical and photoelectric properties of the drop-casting film of Eu13 indicate its great potential in optoelectric device applications.

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 Au 12 tri-octahedral kernel surrounded by two Au 2 (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.