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Diamond‐like (DL) metal chalcogenides have attracted significant attention in recent years because of their complex structural compositions and exceptional nonlinear optical (NLO) capabilities in the infrared (IR) range. Despite notable advancements in this field, there is still a lack of systematic research on high‐performance and simply composed IR‐NLO chalcogenides with DL structures. In this study, the insightful structural characteristics and IR‐NLO properties of a ternary Ag‐based chalcogenide Ag2GeS3 are investigated for the first time at both experimental and theoretical levels. The compound belongs to the non‐centrosymmetric Cmc21 space group (No.36) and displays a 3D DL structure comprising highly oriented [AgS4] and [GeS4] tetrahedra. Due to its distinct structure, the compound may produce significant second harmonic generation (SHG) response (5.6 × AgGaS2 at 2050 nm), the biggest value reported among Ag‐based IR‐NLO chalcogenides to date, and phase matchability in the IR range with a calculated birefringence of Δn = 0.09 at 2050 nm. According to theoretical calculations, the combined impacts of the distorted [AgS4] and [GeS4] NLO‐active motifs inside the 3D DL framework provide the SHG tensor d24 of Ag2GeS3 at 51.9 pm V−1 at 2050 nm. The prospective uses of Ag2GeS3 in the field of IR‐NLO are highlighted in this work. [ABSTRACT FROM AUTHOR]

The coupling electrosynthesis involving CO2 upgrade conversion is of great significance for the sustainable development of the environment and energy but is challenging. Herein, we exquisitely constructed the self‐supported bimetallic array superstructures from the Cu(OH)2 array architecture precursor, which can enable high‐performance coupling electrosynthesis of formate and adipate at the anode and the cathode, respectively. Concretely, the faradaic efficiencies (FEs) of CO2‐to‐formate and cyclohexanone‐to‐adipate conversion simultaneously exceed 90% at both electrodes with excellent stabilities. Such high‐performance coupling electrosynthesis is highly correlated with the porous nanosheet array superstructure of CuBi alloy as the cathode and the nanosheet‐on‐nanowire array superstructure of CuNi hydroxide as the anode. Moreover, compared to the conventional electrolysis process, the cell voltage is substantially reduced while maintaining the electrocatalytic performance for coupling electrosynthesis in the two‐electrode electrolyzer with the maximal FEformate and FEadipate up to 94.2% and 93.1%, respectively. The experimental results further demonstrate that the bimetal composition modulates the local electronic structures, promoting the reactions toward the target products. Prospectively, our work proposes an instructive strategy for constructing adaptive self‐supported superstructures to achieve efficient coupling electrosynthesis. [ABSTRACT FROM AUTHOR]

The goal of this study was to investigate how the electron-donating capability around the lower valent metal ion and the electron-accepting capability of the higher valent metal ion influence metal to metal charge transfer (MMCT) properties in mixed-valence complexes. A series of trinuclear ruthenium complexes represented as [Ru2(ap-4-Me)3(CH3COO)N≡CRuCpMex(dppe)][PF6] (CpMex = polymethylcyclopentadienyl, x = 0, 1, and 5; and dppe = 1, 2-bis(diphenylphosphino)ethane, ap-4-Me = 2-anilino-4-methylpyridine) and their one-electron oxidized products were synthesized and fully characterized. The UV–vis-NIR spectra confirmed that as the electron donor character of the CpMex(dppe)RuCN fragment enhanced or the electron-accepting capability of the higher valent diruthenium cluster increased, the RuII → Ru V2 or Ru VI2 Ru2 MMCT bands shifted to lower energies, which was supported by TDDFT calculations. [ABSTRACT FROM AUTHOR]