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The systematic induction of structural defects at the atomic level is crucial to metal nanocluster research because it endows cluster‐based catalysts with highly reactive centers and allows for a comprehensive investigation of viable reaction pathways. Herein, by substituting neutral phosphine ligands for surface anionic thiolate ligands, we establish that one or two Au3 triangular units can be successfully introduced into the double‐stranded helical kernel of Au44(TBBT)28, where TBBT=4‐tert‐butylbenzenethiolate, resulting in the formation of two atomically precise defective Au44 nanoclusters. Along with the regular face‐centered‐cubic (fcc) nanocluster, the first series of mixed‐ligand cluster homologues is identified, with a unified formula of Au44(PPh3)n(TBBT)28−2n (n=0–2). The Au44(PPh3)(TBBT)26 nanocluster having major structural defects at the bottom of the fcc lattice demonstrates superior electrocatalytic performance in the CO2 reduction to CO. Density functional theory calculations indicate that the active site near the defects significantly lowers the free energy for the *COOH formation, the rate‐determining step in the whole catalytic process. [ABSTRACT FROM AUTHOR]

Two new ternary Cd(II) coordination polymers, [Cd2(L)(tbip)2]n (1) and {[Cd(L)0.5(1,4-NDC)]·0.4H2O}n (2) (H2tbip = 5-tert-butylisophthalic acid, 1,4-H2NDC = 1,4-naphthalenedicarboxylic acid and L = 1,4-bis(2-ethylbenzimidazol-1-ylmethyl)benzene), were hydrothermally synthesized and characterized via single-crystal X-ray diffraction, IR spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric analysis. 1 is a 1-D linear chain, while 2 exhibits a 3-D framework, which can be defined as a 3-D xah (sqc320) topology with the Schläfli symbol of {42.62.82}{46.64}. 1 and 2 remained stable in a pH range of 4.0–13.0 and 3.0–13.0, respectively. 1 and 2 displayed excellent luminescent sensing abilities for Fe3+ ions and tetracycline with high sensitivity and selectivity. [ABSTRACT FROM AUTHOR]

Exploring new noncovalent bonding motifs with reversibly tunable binding affinity is of fundamental importance in manipulating the properties and functions of supramolecular self‐assembly systems and materials. Herein, for the first time, we demonstrate a unique visible‐light‐switchable telluro‐triazole/triazolium‐based chalcogen bonding (ChB) system in which the Te moieties are connected by azobenzene cores. The binding strengths between these azo‐derived ChB receptors and the halide anions (Cl−, Br−) could be reversibly regulated upon irradiation by visible light of different wavelengths. The cis‐bidentate ChB receptors exhibit enhanced halide anion binding ability compared to the trans‐monodentate receptors. In particular, the telluro‐triazolium‐based ChB receptor can achieve both high and significantly photoswitchable binding affinities for halide anions, which enable it to serve as an efficient photocontrolled organocatalyst for ChB‐assisted halide abstraction in a Friedel–Crafts alkylation benchmark reaction. [ABSTRACT FROM AUTHOR]