Site‐Resolved Two‐Step Relaxation Process in an Asymmetric Dy2 Single‐Molecule Magnet

Elaborate chemical design is of utmost importance in order to slow down the relaxation dynamics in single‐molecule magnets (SMMs) and hence improve their potential applications. Much interest was devoted to the study of distinct relaxation processes related to the different crystal fields of crystallographically independent lanthanide ions. However, the assignment of the relaxation processes to specific metal sites remains a challenging task. To address this challenge, a new asymmetric Dy₂ SMM displaying a well‐separated two‐step relaxation process with the anisotropic centers in fine‐tuned local environments was elaborately designed. For the first time a one‐to‐one relationship between the metal sites and the relaxation processes was evidenced. This work sheds light on complex multiple relaxation and may direct the rational design of lanthanide SMMs with enhanced magnetic properties.     

The application of metal-organic frameworks in electrocatalytic nitrogen reduction

In recent years, the research of nitrogen reduction reaction (NRR) under ambient conditions has attracted wide attention for their relatively low energy consumption, in which rational design of electrocatalysts is the key to achieve high-performance NRR. Metal-organic frameworks (MOFs), as a new kind of porous material, have been intensively studied in the past few decades owing to not only their structural versatility and tunability but also intrinsic porosity. Due to their structural features, MOFs also have potential applications in mild condition electrocatalysis of NRR. In this review, the recently experimental and theoretical studies of MOFs in NRR electrocatalysts are briefly summarized.     

Electro-assisted Molecular Assembly Giving Atomic-Scale Catalytic Active-Site Detection

The artificially accurate design of nonmetal electrocatalysts’ active site has been a huge challenge because no pure active species with the specific structure could be strictly controlled by traditional synthetic methods. Species with a multiconfiguration in the catalyst hinder identification of the active site and the subsequent comprehension of the reaction mechanism. We have developed a novel electro-assisted molecular assembly strategy to obtain a pure pentagon ring on perfect graphene avoiding other reconstructed structures. More importantly, the active atom was confirmed by the subtle passivation process as the topmost carbon atom. Recognition of the carbon-defect electrocatalysis reaction mechanism was first downsized to the single-atom scale from the experimental perspective. It is expected that this innovative electro-assisted molecular assembly strategy could be extensively applied in the active structure-controlled synthesis of nonmetal electrocatalysts and verification of the exact active atom.     

On the metabolites produced by Colletotrichum gloeosporioides a fungus proposed for the Ambrosia artemisiifolia biocontrol; spectroscopic data and absolute configuration assignment of colletochlorin A

Ambrosia artemisiifolia L. is responsible for serious allergies induced on humans. Different approaches for its control were proposed during the COST Action FA1203 “Sustainable management of Ambrosia artemisiifolia in Europe” (SMARTER). Fungal secondary metabolites often show potential herbicidal activity. Three phytotoxins were purified from the fungal culture filtrates of Colletotrichum gloeosporioides, isolated from infected leaves of A. artemisiifolia. They were identified by spectroscopic and chemical methods as colletochlorin A, orcinol and tyrosol (1, 2 and 3). The absolute configuration 6’R to colletochlorin A was assigned for the first time applying the advanced Mosher’s method. When assayed by leaf-puncture on A. artemisiifolia only 1 caused the appearance of large necrosis. The same symptoms were also induced by 1 on ambrosia plantlets associated with plant wilting. On Lemna minor, colletochlorin A caused a clear fronds browning, with a total reduction in chlorophyll content.     

Smarandache函数在两数列上的下界估计

设S(n)是Smarandache函数,其中n是一正整数.讨论Smarandache函数S(n)在数列F((2k),1)=F(n,1)=n2n+1(n=2k)与数列G(2n,1)=(2n)2n+1上的下界估计.基于初等方法证明了:当偶数n≥6时,有S(F((2k),1))=S(F(n,1))≥6×2n+1;当n≥4时,有S(G(2n,1))≥6×2n+1.     

Stable Heterometallic Cluster‐Based Organic Framework Catalysts for Artificial Photosynthesis

A series of stable heterometallic Fe₂M cluster‐based MOFs ( NNU‐31‐M , M=Co, Ni, Zn) photocatalysts are presented. They can achieve the overall conversion of CO₂ and H₂O into HCOOH and O₂ without the assistance of additional sacrificial agent and photosensitizer. The heterometallic cluster units and photosensitive ligands excited by visible light generate separated electrons and holes. Then, low‐valent metal M accepts electrons to reduce CO₂, and high‐valent Fe uses holes to oxidize H₂O. This is the first MOF photocatalyst system to finish artificial photosynthetic full reaction. It is noted that NNU‐31‐Zn exhibits the highest HCOOH yield of 26.3 μmol g^?1 h^?1 (selectivity of ca. 100 %). Furthermore, the DFT calculations based on crystal structures demonstrate the photocatalytic reaction mechanism. This work proposes a new strategy for how to design crystalline photocatalyst to realize artificial photosynthetic overall reaction.     

Comparison of Penta and Tetra-pyridyl Cobalt-based Catalysts for Water Reduction: H2 Production Cycle,Solvent Response and Reduction Free Energy

Understanding water reduction towards H₂ generation is crucial to overcome today's renewable energy obstacles. Previous studies have shown the superior H₂ production performances of Cobalt based penta-pyridyl (CoaPPy) and tetra-pyridyl (CoaTPy) complexes in solution. We investigate H₂ production cycles of CoaPPy and CoaTPy complexes immersed in water solution by means of Ab-initio Molecular Dynamics and Density Functional Theory. We monitor dynamic properties of the systems, solvent response and structural changes occurring in the catalysts, by simulating all intermediate steps of the H₂ production cycle. Reduction free energies and reorganization energies are calculated. Our results show that, following the first electron injection, H₂ production proceeds with the singlet spin state. Following the first electron insertion, we observe a significant rearrangement of the hydrogen bonding network in the first solvation shell. The cobalt center turns out to be more accessible for the surrounding water molecules in the case of CoaTPy at all the intermediate steps, which explains its higher catalytic performance over CoaPPy. Following the first reduction reaction, a larger gain in reduction free energy is estimated for CoaTPy with respect to CoaPPy, with a difference of 0.14 eV, in line with the experiments. For the second reduction, instead, CoaPPy shows more negative reduction potential, by 0.41 eV.     

Study of nucleon-nucleon and alphanucleon elastic scattering by the Manning-Rosen potential

Although often used in molecular dynamics, in this work the Manning–Rosen potential is parameterized to compute the scattering phase shifts for the nucleon–nucleon and the alpha-nucleon systems by exploiting the standard phase function method. We obtain excellent agreement in phase shifts with the more sophisticated calculations up to partial waves ${\ell }=2.$