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Bi‐based electrocatalysts have attracted high attention due to their high selectivity for formate, low cost, and high biocompatibility. Surface modification with halides can adjust the surface charge distribution of metal catalysts, thereby regulating the binding force of the intermediate. Organic‐inorganic hybrid bismuth halides provide an alternative, especially low dimensional structures. Herein, zero‐dimensional hybrid bismuth halides containing Bi4I16 units (denoted as Bi4I16) was recommended as pre‐catalyst due to the Bi ⋅ ⋅ ⋅ Bi spacing in Bi4I16 is 4.760 Å, nearly equaling to the Bi ⋅ ⋅ ⋅ Bi spacing in rhombohedral Bi (4.750 Å). The equal spacing may be more beneficial for the electricity‐driven in situ conversion and rearrangement of Bi atoms in the catalytic process. As a contrast, zero‐dimensional bismuth halide containing Bi2I9 units (denoted as Bi2I9) with shorter Bi ⋅ ⋅ ⋅ Bi spacing (4.2415 Å) was prepared. The working electrode prepared by Bi4I16 ink was measured for CO2RR, and the partial formate current density can reach 8.2 mA cm−2 at −1.1 V vs RHE. The Bi4I16 catalyst delivers a maximum Faradaic Efficiency (FE, ~80 %) for formate at −0.86 V vs RHE and maintain a FE higher than 78.5 % after 16 h. [ABSTRACT FROM AUTHOR]

Discrete supertetrahedral clusters of metal chalcogenides are rare because of the difficulty involved in meeting global charge matching between the negative charge of the skeleton and counterion. We present herein the third type of a discrete chalcogenide cluster with a double T3 structure in the compound (HDBN)6[In20S33(DBN)6] (DBN = 1,5-diazabicyclo [4.3.0]-5-nonene), the anion of which features quasi-D3 symmetrical double-T3 In20S33 supertetrahedra with six cornered indium atoms coordinated by DBN molecules. DFT theory calculations of the interaction between host and guest show that this compound may have high kinetic stability and low photoelectric reactivity. [ABSTRACT FROM AUTHOR]

The only feasible access to non‐face‐centered cubic (FCC) copper was by physical vapor deposition under high vacuum. Now, non‐FCC copper is observed in a series of alkynyl‐protected Cu53 nanoclusters (NCs) obtained from solution‐phase synthesis. Determined by single‐crystal X‐ray crystallography, the structures of Cu53(C≡CPhPh)9(dppp)6Cl3(NO3)9 and its two derivatives reveal an ABABC stacking sequence involving 41 Cu atoms. It can be regarded as a mixed FCC and HCP structure, which gives strong evidence that Cu can be arranged in non‐FCC lattice at ambient conditions when proper ligands are provided. Characterization methods including X‐ray absorption fine structure, XPS, ESI‐MS, UV/Vis, Auger spectroscopy, and DFT calculations were carried out. CuII was shown to successively coordinate with introduced ligands and changed to CuI after bonding with phosphine. The following addition of NaBH4 and the aging step further reduced it to the Cu53 NC. [ABSTRACT FROM AUTHOR]

Three genuine supramolecular isomers with an identical formula of [Co(cpna)(H2O)2] (1a, 1b and 1c) [H2cpna = 5-(4′-carboxyl-phenyl) nicotinic acid] have been synthesized by adjusting the relative molar ratio of Y-shaped ligand H2cpna : CoCl2 under solvothermal conditions. Isomer 1a possesses a two-dimensional (2D) 63-hcb layer, in which the central Co(ii) adopts trigonal bipyramidal geometry. 1b and 1c contain the same edge-shared dimeric SBUs, which are further ligated by cpna2− ligands to form 2D (3,6)-connected (43)2(46·66·83)-kgd layers and a 3D (3,6)-connected (4·62)2(42·610·83)-rtl net, respectively. The coordination modes of the cpna2− ligand in 1b and 1c are the same, indicating that only the difference in the dihedral angles of the pyridine and phenyl rings contributes to different isomers. Magnetic investigation indicates ferromagnetic interactions between Co(ii) ions in edge-shared dimeric SBUs. [ABSTRACT FROM AUTHOR]

Four novel coordinationpolymers based on asymmetric triangular5-(4′-carboxylphenyl) nicotinic acid (H2cpna), namely,Ni(cpna)(H2O)2(1), M2(cpna)2(H2O)3·0.5H2O·DMF [M = Ni for (2), Co for (3)]and Ni3(Hcpna)2(cpna)2(H2O)4·2H2O (4), have been synthesizedunder solvothermal conditions. All of the four compounds contain lownuclear metal clusters as secondary building units (SBUs). Complex 1exhibits two-dimensional (3,6)-connected (43)2(46.66.83)-kgdtopology, in which cpna ligands and edge-shared dinuclear SBUs actas 3-connected and 6-connected nodes, respectively. Compounds 2and 3are constructed by corner-shared dinuclearSBUs and show an unprecedented (3,6)-connected chiral (42.6)2(44.62.88.10)-anh(flu-3, P6222) topology. In 4, linear trimers are ligated by sixcpna ligands to form a planar (43)2(46.66.83)-kgdlayer, and adjacentlayers are further linked by Hcpna–ligands throughNi–O and Ni–N bonds to form three-dimensional (3,8)-connected(43)2(46.618.84)-tfz-dnet. Both 1and 4crystallize in the triclinic crystal system with symmetric spacegroup P̅1, which result in an equal ratio of(R)- and (S)-cpna isomers. Isostructural 2and 3crystallize in a trigonal crystal systemwith the chiral space group P3221, anda single crystal contains a sole optical isomer of cpna, althoughbulk crystals are a racemic mixture. Variable-temperature magneticsusceptibility measurements reveal ferromagnetic coupling of edge-shareddimers in 1, antiferromagnetic coupling of corner-shareddimers in 2and 3, and ferrimagnetic couplingof linear trimers in 4. [ABSTRACT FROM AUTHOR]