Electrically Switchable Magnetic Molecules: Inducing a Magnetic Coupling by Means of an External Electric Field in a Mixed‐Valence Polyoxovanadate Cluster

Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed‐valence polyoxometalate (POM) [GeV₁₄O₄₀]^8? (in short V₁₄) by using both a t‐J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest‐neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have led to similar results, emphasizing that the sharp spin transition induced by the electric field in the V₁₄ system is a robust phenomenon, intramolecular in nature, and barely influenced by small changes on the external structure.     

Using a Novel and Easy-to-Use Sandwich Structure Device to Evaluate the Cooling Properties of Cool Materials

A number of cool materials have been designed and used in hot weather to minimize the heat coming from sunlight. Traditionally, solar reflectance and infrared emittance were measured to characterize the cooling properties of cool materials. However, these methods could represent the cooling property only indirectly. In this work, a sandwich structure device that can straightforwardly measure the cooling properties of cool materials was designed. Two cool materials, including high-density polyethylene (HDPE) and polyvinyl chloride (PVC), were selected to verify the device. For the purpose of comparison, UV-vis-NIR spectral characterization was also used to evaluate the cooling properties of the selected materials. The results, especially for the HDPE/Green 260 composite sample, which presents much lower solar reflectance but better cooling property, indicated that the cooling properties cannot be entirely represented by only the reflectance or transmittance, and the sandwich structure device was able to make up for this deficiency.     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

Azobenzene‐Functionalized Cage Silsesquioxanes as Inorganic–Organic Hybrid,Photoresponsive, Nanoscale,Building Blocks

Mono‐ and octa‐azobenzene‐functionalized cage silsesquioxanes were easily synthesized by the reaction of 4‐bromoazobenzene with monovinyl‐substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited‐state energies obtained from time‐dependent density functional theory (TDDFT) and the CAM‐B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene‐functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue‐light emission.     

Two-dimensional topological semimetals

The field of two-dimensional topological semimetals, which emerged at the intersection of two-dimensional materials and topological materials, has been rapidly developing in recent years. In this article, we briefly review the progress in this field. Our focus is on the basic concepts and notions, in order to convey a coherent overview of the field. Some material examples are discussed to illustrate the concepts. We discuss the outstanding problems in the field that need to be addressed in future research.     

Investigation of mononuclear,dinuclear, and trinuclear transition metal (II) complexes derived from an asymmetric Salamo‐based ligand possessing three different coordination modes

A new asymmetric Salamo‐based ligand H₂L was synthesized using 3‐tert‐butyl‐salicylaldehyde and 6‐methoxy‐2‐[O‐(1‐ethyloxyamide)]‐oxime‐1‐phenol. By adjusting the ratio of the ligand H₂L and Cu (II), Co (II), and Ni (II) ions, mononuclear, dinuclear, and trinuclear transition metal (II) complexes, [Cu(L)], [{Co(L)}₂], and [{Ni(L)(CH₃COO)(CH₃CH₂OH)}₂Ni] with the ligand H₂L possessing completely different coordination modes were obtained, respectively. The optical spectra of ligand H₂L and its Cu (II), Co (II) and Ni (II) complexes were investigated. The Cu (II) complex is a mononuclear structure, and the Cu (II) atom is tetracoordinated to form a planar quadrilateral structure. The Co (II) complex is dinuclear, and the two Co (II) atoms are pentacoordinated and have coordination geometries of distorted triangular bipyramid. The Ni (II) complex is a trinuclear structure, and the terminal and central Ni (II) atoms are all hexacoordinated, forming distorted octahedral geometries. Furthermore, optical properties including UV–Vis, IR, and fluorescence of the Cu (II), Co (II), and Ni (II) complexes were investigated. Finally, the antibacterial activities of the Cu (II), Co (II), and Ni (II) complexes were explored. According to the experimental results, the inhibitory effect was found to be enhanced with increasing concentrations of the Cu (II), Co (II), and Ni (II) complexes.     

Properties and applications of precision oligomer materials; where organic and polymer chemistry join forces

Precise oligomeric materials constitute a growing area of research with implications for various applications as well as fundamental studies. Notably, this field of science which can be termed macro-organic chemistry, draws inspiration from both traditional polymer chemistry and organic synthesis, combining the molecular precision of organic chemistry with the materials properties of macromolecules. Discrete oligomers enable access to unprecedented materials properties, for example, in self-assembled structures, crystallization, or optical properties. The degree of control over oligomer structures resembles many biological systems and enables the design of materials with tailored properties and the development of fundamental structure–property relationships. This Review highlights recent developments in macro-organic chemistry from synthetic concepts to materials properties, with a focus on self-assembly and molecular recognition. Finally, an outlook for future research directions is provided.     

Methyl orange degradation enhanced by hydrogen spillover onto platinum nanocatalyst surface

Following a thermal reduction method, platinum nanoparticles were synthesized and stabilized by polyvinylpyrrolidone. The colloidal platinum nanoparticles were stable for more than 3 months. The micrograph analysis unveiled that the colloidal platinum nanoparticles were well dispersed with an average size of 2.53 nm. The sol–gel‐based inverse micelle strategy was applied to synthesize mesoporous iron oxide material. The colloidal platinum nanoparticles were deposited on mesoporous iron oxide through the capillary inclusion method. The small‐angle X‐ray scattering analysis indicated that the dimension of platinum nanoparticles deposited on mesoporous iron oxide (Pt‐Fe₂O₃) was 2.64 nm. X‐ray photoelectron spectroscopy (XPS) data showed that the binding energy on Pt‐Fe₂O₃ surface decreased owing to mesoporous support–nanoparticle interaction. Both colloidal and deposited platinum nanocatalysts improved the degradation of methyl orange under reduction conditions. The activation energy on the deposited platinum nanocatalyst interface (2.66 kJ mol^?1) was significantly lowered compared with the one on the colloidal platinum nanocatalyst interface (40.63 ± 0.53 kJ mol^?1).     

A Theoretical study on the charge and discharge states of Na-ion battery cathode material,Na1+xFePO4F

Na₂FePO₄F is a promising cathode material for a Na-ion battery because of its high electronic capacity and good cycle performance. In this work, first principle calculations combined with cluster expansion and the Monte Carlo method have been applied to analyze the charge and discharge processes of Na₂FePO₄F by examining the voltage curve and the phase diagram. As a result of the density functional theory calculation and experimental verification with structural analysis, we found that the most stable structure of Na_1.5FePO₄F has the P2₁/b11 space group, which has not been reported to date. The estimated voltage curve has two clear plateaus caused by the two-phase structure composed of P2₁/b11 Na_1.5FePO₄F and Pbcn Na₂FePO₄F or Na₁FePO₄F and separated along the c-axis direction. The phase diagram shows the stability of the phase-separated structure. Considering that Na₂FePO₄F has diffusion paths in the a- and c-axis directions, Na₂FePO₄F has both innerphase and interphase diffusion paths. We suggest that the stable two-phase structure and the diffusion paths to both the innerphase and interphases are a key for the very clear plateau. We challenge to simulate a nonequilibrium state at high rate discharge with high temperature by introducing a coordinate-dependent chemical potential. The simulation shows agreement with the experimental discharge curve on the disappearance of the two plateaus. © 2018 Wiley Periodicals, Inc.     

In vitro anti‐proliferative and in silico docking studies of heteroleptic copper(II) complexes of pyridazine‐based ligands and ciprofloxacin

Three heteroleptic copper(II) complexes of the type [Cu(L^1–3)(cf)(ClO₄)] ( 1 – 3 ), where cf = ciprofloxacin, have been synthesized using pyridazine‐based ligands 3‐chloro‐6‐(salicylidenehydrazinyl)pyridazine (HL¹), 3‐chloro‐6‐(4‐diethylaminosalicylidenehydrazinyl)pyridazine (HL²) and 3‐chloro‐6‐(5‐bromosalicylidenehydrazinyl)pyridazine (HL³). Electronic spectral data and magnetic moment values suggest octahedral geometry for the synthesized copper(II) complexes. Electrochemical data of the copper(II) complexes present an irreversible one‐electron reduction wave in the cathodic potential region (E_pc) between ?0.631 and ?0.670 V. Frontier molecular orbital calculations were carried out, and the obtained low‐energy gap supports the bio‐efficacy of the complexes. All the complexes were screened for their in vitro cytotoxicity activity against three human cancerous (breast adenocarcinoma (MCF‐7), hepatoma (HepG‐2) and cervical (HeLa)) and one non‐cancerous (non‐tumorigenic human dermal fibroblast (NHDF)) cell lines using MTT assay, in which complex 2 exhibited higher activity. The apoptosis induction by the complexes was analysed using the Hoechst dye staining method with MCF‐7 cell line, which indicates higher apoptotic activity of complex 2 . A molecular docking study was carried out to ascertain the binding affinity of the synthesized heteroleptic copper(II) complexes with phosphoinositide 3‐kinase gamma (PI3Kγ) receptor.