The protocols of the crystalline sponge method, particularly those in the soaking, data collection and refinement processes, are considerably improved to give reliable structural information.
The [Au37(PPh3)10(SR)10X2](+) nanocluster (where SR = thiolate and X = Cl/Br) was theoretically predicted in 2007, but since then, there has been no experimental success in the synthesis and structure determination. Herein, we report a kinetically controlled, selective synthesis of [Au37(PPh3)10(SC2H4Ph)10X2](+) (counterion: Cl(-) or Br(-)) with its crystal structure characterized by X-ray crystallography. This nanocluster shows a rod-like structure assembled from three icosahedral Au13 units in a linear fashion, consistent with the earlier prediction. The optical absorption and the electrochemical and catalytic properties are investigated. The successful synthesis of this new nanocluster allows us to gain insight into the size, structure, and property evolution of gold nanoclusters that are based upon the assembly of icosahedral units (i.e., cluster of clusters). Some interesting trends are identified in the evolution from the monoicosahedral [Au13(PPh3)10X2](3+) to the bi-icosahedral [Au25(PPh3)10(SC2H4Ph)5X2](2+) and to the tri-icosahedral [Au37(PPh3)10(SC2H4Ph)10X2](+) nanocluster, which also points to the possibility of achieving even longer rod nanoclusters based upon assembly of icosahedral building blocks.
By using a controllable pillared-layer
method, a novel visible-light
responsive metal–organic framework (MOF) photocatalyst NNU-36
has been rationally constructed. The synthesized NNU-36 is of broad-range
visible light absorption and good chemical stability which are beneficial
to its application of photocatalysis. Photocatalytic experiments reveal
that NNU-36 is highly efficient for Cr(VI) reduction and dye degradation
in aqueous solution under visible light irradiation. Control experiments
show that the pH value is vital for Cr(VI) reaction, and meanwhile,
the use of hole scavenger of methanol promotes the photocatalytic
reduction significantly. It has been also demonstrated that NNU-36
is efficient for dye degradation, in which the introduction of hydrogen
peroxide (H2O2) significantly enhances the photocatalytic
efficiency of dye degradation. This study illustrates that the introduction
of hole scavengers or oxidants in the MOF-mediated photocatalytic
reaction is a feasible approach to enhance the catalytic efficiency
by suppressing the recombination of photoexcited electron–hole
pairs in MOFs photocatalysts.
A new three-dimensional microporous MOF has been constructed using a highly conjugated anthracene-based ligand. The rarely occurring long-range π-stacking of the ligand in the form of a zigzag chain has been found in the MOF structure, which provides not only a new charge transport pathway with high electrical conductivity of 1.3 (±0.5) × 10(-3) S cm(-1) but also an electroluminescence property with an emission centred at 575 nm.
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