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A d10 Cu(I) two‐dimensional (2D) metal–organic framework (MOF) with chemical formulas, {[Cd(L)(tcm)(H2O)]⋅2H2O}n (1) (L = 1,3,5‐tris(4‐pyridylethynyl)benzene; tcm−1 = tricyanomethanide) was synthesized and structurally characterized by single crystal X‐ray diffraction method. In 1, the coordination geometry of Cu(I) ion is distorted tetrahedral coordinated to four N atoms from three L and one tcm− ligands. A 2D puckered honeycomb‐like layer is formed via the bridges of Cu(I) ions and L ligands with tris‐monodentate coordination mode. Two 2D layers are mutually interpenetrated via the π–π stacking interaction between benzene ring of L ligand and pyridyl ring of neighboring L ligand to form a two‐fold interpenetrated 2D net and then arranged orderly to construct its 3D supramolecular network. Thermal stability and in‐situ temperature‐dependent structural variations of 1 are performed by TG analysis associated with temperature‐dependent PXRD measurement. The water vapor ad‐/de‐sorption isotherm and CO2 adsorption isotherm of 1 are measured and discussed. [ABSTRACT FROM AUTHOR]

A 3Fe4S cluster related to M‐cluster of Mo‐nitrogenase is reported. [K(THF)5][Fe3(μ‐bdt)2(μ‐PPh2)(CO)5] (1) is synthesized from photo‐assisted structural rearrangement of [K(THF)2][(μ,κ2‐bdt)Fe2(μ‐PPh2)(CO)5] under visible light irradiation. The molecular structure of 1 consists of a Fe3 core bearing one dithiolate bridge and the second dithiolate group capping onto the metallic plane. The structural motif of 1 is analogous to that of Mo‐participated 3Fe4S unit in M‐cluster of Mo‐nitrogenase, with the similar Fe‐Fe and Fe‐S bond distances. Upon protonation in 193 K, a Fe‐hydride species (1H) is generated and characterized to possess the bridging hydride group (δ = −12.57 ppm) by 1H‐NMR spectroscopy and DFT calculation. In CH3CN solution, complex 1 exhibits a reversible reduction and oxidation process at E1/2red = −1.94 V and E1/2ox = −0.18 V, respectively, at 273 K. The reduction behavior of 1 in CH2Cl2 solution at 243 K displays a slight modification in the presence of trifluoroacetic acid, revealing a moderate anodic potential shift (~50 mV). The current amplitude of the reduction wave is linearly increased with the increasement of acid added, indicative of the catalytic event. [ABSTRACT FROM AUTHOR]

Two d10 M(II) (M = Cd and Zn) coordination polymers (CPs) with chemical formulas, {[Cd(L1)(NCS)2(H2O)]⋅C2H5OH}n(1), and {[Zn(L1)(NCS)2]⋅C2H5OH⋅0.5H2O}n(2) (L1 = 1,3,5‐tris(4‐pyridylsulfanylmethyl)‐2,4,6‐trimethylbenzene) were synthesized and structurally characterized by single‐crystal x‐ray diffraction method. In compound 1, the coordination environment of Cd(II) ion is distorted octahedral bonded to three nitrogen donors from three L1 ligands located in a facial‐position, two nitrogen donors from NCS− and one water molecule. The L1 acts as a bridge ligand with tris‐monodentate coordination mode in a cis‐cis‐cis structural conformation, connecting the Cd(II) to form a two‐dimensional (2D) zigzag‐like layered metal‐organic frameworks. Adjacent 2D layers are then arranged orderly in an ABAB manner to complete its three‐dimensional (3D) supramolecular architecture. In compound 2, the coordination environment of Zn(II) ion is distorted tetrahedral bonded to two nitrogen donors from two L1 ligands and two nitrogen donors from two NCS− ligands. The L1 acts as a bridge ligand with bis‐monodentate coordination mode in a cis‐cis‐cis structural conformation, connecting the Zn(II) ions to form a one‐dimensional (1D) zigzag‐like polymeric chain. Adjacent chains are arranged orderly in an alternate ABAB manner to generate a 2D framework and then further arranged in an AAA manner to complete its 3D supramolecular architecture. The structural characterization as well as thermal‐stability and solvents de‐/ad‐sorption behavior of 1 and 2 are studied and discussed in details. [ABSTRACT FROM AUTHOR]

Four low‐spin {FeNO}6 complexes, [Fe(NO)(PS2)(PS2H)] (1, PS2H2 = bis(2‐dimercaptophenyl)phenylphosphine) with a pendant thiol, [Fe(NO)(PS2)(PS2CH3)] (2) bearing a pendant thioether, and [Fe(NO)(PS2)(RPS)] (RH, 4a; RTMS, 4b) without the noncovalent thiol/thioether group are spectroscopically and structurally characterized. In comparisons of the νNO, absorption energy in UV/vis spectra and structural parameters from single X‐ray diffraction studies, the four iron‐nitrosyl‐thiolato compounds share similarity in electronic structure. Complex 1 with a pendant thiol leads to NO and HNO production upon exposure to the light. Photolysis of 2 bearing a pendant thioether only affords NO. Effective detection of HNO or NO from 1 or 2 is achieved by the employment of [MnIII(TMSPS3)(DABCO)]. In contrast, 4a and 4b show inertness toward visible‐light stimulus. Photolysis and having pendant thiol/thioether group play key roles in NO production from these iron‐nitrosyl‐thiolato complexes, that is, the Fe‐NO bond is weakened by exposure to light and the noncovalent SH of 1 or SCH3 of 2 can serve as an incoming ligand to interact with Fe atom, resulting in a transient with intramolecular [RS⋅⋅⋅Fe⋅⋅⋅NO] interaction (RH and CH3) which could facilitate NO dissociation. [ABSTRACT FROM AUTHOR]

C‐shaped ortho‐benzodipyrrole‐based A‐DNBND‐A non‐fullerene acceptors (NFAs), derived from the removal of the A′ thiadiazole moiety in Y6, emerge as a new class of structurally simplified A‐D‐A‐type NFAs. In this work, a selenium‐substitution strategy is applied to the central DNBND ladder‐π‐core, yielding asymmetric CB‐Se and symmetric CB‐2Se. Asymmetric CB‐Se demonstrates a less ordered 3D trapezoid‐like packing structure, which promotes a more favorable intermixed donor‐acceptor morphology with PM6 polymer, achieving a higher power conversion efficiency (PCE) of 17.87% in organic photovoltaics (OPVs). This value represents the highest reported value among the selenium‐incorporated A‐D‐A‐type NFAs. Symmetric CB‐2Se forms a kaleidoscope‐like 3D single‐crystal structure with enhanced intermolecular interactions. This enables the development of a single‐crystal‐like solution‐processed thin film, which transitions from a kinetically trapped face‐on π–π stacking orientation to a thermodynamically stable edge‐on configuration upon thermal annealing. The CB‐2Se‐based organic field‐effect transistor (OFET) achieved a remarkable electron mobility of 1.18 cm2 V−1 s−1 with exceptional n‐type air stability, which outperformed the corresponding A‐DNA′ND‐A‐type Y6‐based materials by two orders magnitudes and represents the highest reported value for solution‐processed n‐type OFETs utilizing A‐D‐A‐type small molecules. [ABSTRACT FROM AUTHOR]

Two d10 M(II) (M = Cd and Zn) coordination polymers (CPs) with chemical formulas, {[Cd(L1)(NCS)2(H2O)]⋅C2H5OH}n(1), and {[Zn(L1)(NCS)2]⋅C2H5OH⋅0.5H2O}n(2) (L1 = 1,3,5‐tris(4‐pyridylsulfanylmethyl)‐2,4,6‐trimethylbenzene) were synthesized and structurally characterized by single‐crystal x‐ray diffraction method. In compound 1, the coordination environment of Cd(II) ion is distorted octahedral bonded to three nitrogen donors from three L1 ligands located in a facial‐position, two nitrogen donors from NCS− and one water molecule. The L1 acts as a bridge ligand with tris‐monodentate coordination mode in a cis‐cis‐cis structural conformation, connecting the Cd(II) to form a two‐dimensional (2D) zigzag‐like layered metal‐organic frameworks. Adjacent 2D layers are then arranged orderly in an ABAB manner to complete its three‐dimensional (3D) supramolecular architecture. In compound 2, the coordination environment of Zn(II) ion is distorted tetrahedral bonded to two nitrogen donors from two L1 ligands and two nitrogen donors from two NCS− ligands. The L1 acts as a bridge ligand with bis‐monodentate coordination mode in a cis‐cis‐cis structural conformation, connecting the Zn(II) ions to form a one‐dimensional (1D) zigzag‐like polymeric chain. Adjacent chains are arranged orderly in an alternate ABAB manner to generate a 2D framework and then further arranged in an AAA manner to complete its 3D supramolecular architecture. The structural characterization as well as thermal‐stability and solvents de‐/ad‐sorption behavior of 1 and 2 are studied and discussed in details. [ABSTRACT FROM AUTHOR]