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Precisely modulating the spatial charge migration/separation constitutes the central issue in dictating the solar conversion efficiency of photoelectrochemical (PEC) cells, whereas it still remains a grand challenge. Here, we conceptually demonstrate the construction of hierarchically ordered metal oxide (MO)/transition-metal chalcogenide quantum dots (TMC QDs) multilayered heterostructured photoanodes, that is, MO/[TMC QDs(+)/TMC QDs(-)]

The fabrication of highly efficient and sustainable electrocatalysts used for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is exceedingly challenging and warranted for overall water splitting. In this work, we successfully synthesized a series of metal-organic frameworks (MOFs), namely, as Fe2M-MOF (M = Fe, Co, Ni, Zn, Mn; H4L = 3,3,5,5'-azoxybenzenetetracarboxylic acid) under a simple and mild condition, in which the Fe3 cluster as a basic building unit was replaced by the second kind of metal center; at the same time, a redox-active organic linker was adopted. The Fe2M-MOF system as a multifunctional catalyst realizes great improvement of the OER and HER performances. Among of them, the Fe2Co-MOF catalyst exhibits an extremely low overpotential of 339 mV at a current density of 10 mA cm-2 and a very small Tafel slope of 36.2 mV dec-1 in an alkaline electrolyte for OER. This result has far exceeded the commercial catalyst IrO2. Meanwhile, Fe2Zn-MOF manifests excellent HER activity with a small overpotential of 221 mV at 10 mA cm-2 and a low Tafel slope of 174 mV dec-1. In addition, the good long-term stability for these catalysts can be evaluated under working conditions. Systematic investigations are used to explain the enhanced electrocatalytic mechanism. In conclusion, we provide a simple and effective strategy for the preparation of multifunctional catalysts for energy conversion applications based on a pristine MOF material with redox-active metal centers and organic linkers.

A metal-organic supramolecular nanobelt was synthesized by quantitative self-assembling terpyridine-functionized tetraphenylethylene (TPE) and Cd2+, which only showed a weak emission both in solution or aggregated state. Nevertheless, nanobelt complex could be transferred to a fluorescence turn-on sensor to S2- by taking advantage of the structural transformation from nanobelt to its fluorescent ligand.

A novel metal–organic ligand (MOL 2) has been prepared by linking two V-shaped bis-terpyridines with one X-shaped tetrakis-terpyridine through the stable connectivity. The complexati...

A highly luminescent porous metal-organic framework Cd3(L)2.5(4-PTZ)(DMF)3, labeled as NBU-9, has been designedly synthesized based on Cd(NO3)2·4H2O and mixed ligands of 4-(1 H-tetrazol-5-yl)pyridine (4-HPTZ) with N-coordinated sites and thiophene-2,5-dicarboxylic acid (H2L) with heteroatomic (S) ring and carboxylate groups in N, N-dimethylformamide (DMF) at 100 °C for 3 days. The interesting result is that this compound NBU-9 can be also obtained via the mixed raw materials of Cd(NO3)2·4H2O, 4-cyanopyridine, NaN3, and H2L under solvothermal condition at a higher temperature of 140 °C for 3 days, involving in situ ligand synthesis of 4-HPTZ. Its structure was indentified by single-crystal X-ray study, powder X-ray diffraction, element analysis, and TGA results. Structural analysis shows that the three-dimensional framework of NBU-9 contains cubic channels of 9.59 × 10.26 A2 covered by a large number of open S- and O-coordinated sites and can be simplified into a 8-connected uninodal eca net with high potential solvent accessible volumes of 34.1%. Its luminescent properties demonstrate that NBU-9 as a multifunctional sensory material realizes the selective detection for the phenylmethanol molecule on the basis of fluorescence quenching mechanism and effectively sensitizing the visible emitting of the Tb3+ cation based on luminescence enhancement.

Upon treatment with ZnII ions, a series of BINOL-bridged bis(phenanthroline) ligands was self-assembled into [M2L3] metallocages, which were carefully characterized by NMR spectroscopy and ESI-MS spectrometry. Among them, a racemic mixture of the BINOL-bridged bis(phenanthrolines) underwent chiral self-sorting to afford two homochiral metallocages. The narcissistic self-sorting process of the metallocages was observed in the complexation reaction of the constitutionally isomeric bis(phenanthrolines) with varying connection positions. Moreover, the endo hydroxyl-functionalized metallocage [Zn2{(S)-L2OH}3] exhibited catalytic activity and substrate selectivity for the Knoevenagel condensation reactions of aromatic tricarbaldehydes with malononitrile.

A shape-persistent metallosupramolecular multirhomboid that inlays a hexarhomboid polygon in a three-lobed flat structure was prepared by means of coordination-driven self-assembly. The key ligands were synthesized by a "reaction on complex" strategy that becomes accessible to troublesome metalloorganic ligand L3. The formation here consists of four different starting components and two metal ions. Complementarity of the shape and size drives molecular puzzling and results in the multicomponent, quantitative self-assembled construct.

The intricate discrete supramolecular architectures via two or more noncovalent interactions are very attractive for chemists. In this paper, a series of homomeric metallo-supramolecular lemniscates were prepared in nearly quantitative yields by assembling either dialkylammonium salt- or benzo-21-crown-7 (B21C7)-containing terpyridyl metallo-organic ligands with Zn2+. Furthermore, the heteromeric analogue could be obtained through two ways: (1) the cooperative interaction of coordination-driven self-assembly and host-guest recognition and (2) the transformation from homodimers to heterodimers driven by host-guest interaction. These supramolecules were characterized by nuclear magnetic resonance (NMR), diffusion-ordered NMR spectroscopy, electrospray ionization mass spectrometry, and two-dimensional (2D) ion-mobility mass spectrometry.

Construction of 3D terpyridine-based metallopolyhedra remains challenging because of the linear coordination geometry of ⟨tpy-MII-tpy⟩ connectivity. A progressive strategy is made by assembling tetranuclear terpyridyl metal–organic ligands to afford a novel regular octahedron, whose structure was established by NMR, electrospray ionization mass spectrometry, traveling-wave ion-mobility mass spectrometry, atomic force microscopy, and transmission electron microscopy. This strategy provides an efficient method for the construction of 3D terpyridine-based metallopolyhedra.