Solvothermal reaction of a TCA (TCA = 4,4',4''-tricarboxytriphenylamine) ligand with Cd(NO3)2 yielded a unique 3D 12-connected metal-organic framework of , which can be simplified as a (3,3,12)-connected 3-nodal net with a Schläfli symbol of {4(16)·6(36)·8(14)}{4(2)·6}2{4(3)}2 based on a 12-connected node of a pentanuclear Cd(ii) cluster and a three-connected organic linker of TCA. Compound exhibits both photoluminescence and proton conductivity. The luminescence properties of originate from the triphenylamine chromophore of the TCA ligand. The proton conductivity of is supposed to be relevant to the structure attributes of . On the one hand, the curved narrow channels lined with a hydrophilic pentanuclear Cd(ii) cluster in can improve the water affinity of framework and facilitate the water absorption under humid conditions. On the other hand, the coordinated water molecules within the pentanuclear Cd(ii) cluster can produce a mobile H(+) proton due to coordination activation. At 80 °C and 85% RH (relative humidity), compound shows the proton conductivity of 1.45 × 10(-6) S cm(-1).
Metal-free carbon materials doped with multiple nonmetal heteroatoms (e. g. N, B, S, P) have emerged as a promising class of electrocatalysts toward oxygen reduction reaction (ORR). Herein, B, N-codoped carbon electrocatalysts are conveniently prepared by use of ZIF-8 precursor, which involves cageencapsulation of PhB(OH) 2 before high-temperature pyrolysis.By modulating the B-doping amount and pyrolysis temperature, an optimal B, N-codoped carbon electrocatalyst toward ORR is achieved, which shows ORR activity (E onset = 0.95 V, and E 1/2 = 0.83 V vs RHE) comparable to the Pt/C benchmark, with a good methanol tolerance and long-term stability.
Under different solvothermal conditions, the reactions of 2-ppds (2-ppds = di[4-(pyridin-2-yl)pyrimidinyl]disulfide) with CuX 2 (X = ClO 4 or Cl) produced markedly different results because of diverse in situ reactions of 2-ppds involving dynamic S-S and C-S bond cleavage. At 90°C, reaction of 2-ppds with Cu(ClO 4 ) 2 in CH 3 CN-CH 2 Cl 2 -mixed solvent yielded a discrete mononuclear complex, [Cu(L1) 2 (ClO 4 )]ClO 4 (1), in which 2-ppds was converted into a zwitterion of L1 (L1 = 4-(pyridin-2-yl)pyrimidin-2-ol) involving C-S bond scission followed by attack of water. At 120°C in DMF-MeOH solvent, reaction of 2-ppds with Cu(ClO 4 ) 2 resulted in transformation to L2 (L2 = 4-(pyridin-2-yl)pyrimidine-2-thiolate) through reductive cleavage of the S-S bond concurrent with reduction of Cu 2? to Cu ? , leading to the formation of a single tetranuclear coordination complex, [Cu 4 (L2) 4 ] (2), that comprises a unique Cu 4 S 4 cluster.When the reaction between 2-ppds and CuCl 2 was carried out at 90°C in CH 3 CN-H 2 O solvent, a discrete coordination complex, [Cu(L3)(H 2 O)Cl]Cl (3), was obtained, resulting from conversion of 2-ppds into L3 (L3 = bis(4-(pyridin-2-yl)pyrimidin-2-yl)sulfane) through extrusion of one S atom from the S-S bond.
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