Remarkably Efficient Photocurrent Generation Based on a [60]Fullerene–Triosmium Cluster/Zn–Porphyrin/Boron–Dipyrrin Triad SAM

A new artificial photosynthetic triad array, a [60]fullerene–triosmium cluster/zinc–porphyrin/boron–dipyrrin complex ( 1 , Os₃C₆₀/ZnP/Bodipy), has been prepared by decarbonylation of Os₃(CO)₈(CN(CH₂)₃Si(OEt)₃)(μ₃‐η²:η²:η²‐C₆₀) ( 6 ) with Me₃NO/MeCN and subsequent reaction with the isocyanide ligand CNZnP/Bodipy ( 5 ) containing zinc porphyrin (ZnP) and boron dipyrrin (Bodipy) moieties. Triad 1 has been characterized by various spectroscopic methods (MS, NMR, IR, UV/Vis, photoluminescence, and transient absorption spectroscopy). The electrochemical properties of 1 in chlorobenzene (CB) have been examined by cyclic voltammetry; the general feature of the cyclic voltammogram of 1 is nine reversible one‐electron redox couples, that is, the sum of those of 5 and 6 . DFT has been applied to study the molecular and electronic structures of 1 . On the basis of fluorescence‐lifetime measurements and transient absorption spectroscopic data, 1 undergoes an efficient energy transfer from Bodipy to ZnP and a fast electron transfer from ZnP to C₆₀; the detailed kinetics involved in both events have been elucidated. The SAM of triad 1 ( 1 /ITO; ITO=indium–tin oxide) has been prepared by immersion of an ITO electrode in a CB solution of 1 and diazabicyclo‐octane (2:1 equiv), and characterized by UV/Vis absorption spectroscopy, water contact angle, X‐ray photoelectron spectroscopy, and cyclic voltammetry. The photoelectrochemical properties of 1 /ITO have been investigated by a standard three‐electrode system in the presence of an ascorbic acid sacrificial electron donor. The quantum yield of the photoelectrochemical cell has been estimated to be 29 % based on the number of photons absorbed by the chromophores. Our triad 1 is unique when compared to previously reported photoinduced electron‐transfer arrays, in that C₆₀ is linked by π bonding with little perturbation of the C₆₀ electron delocalization.     

CAESAR models for developmental toxicity

Background

The new REACH legislation requires assessment of a large number of chemicals in the European market for several endpoints. Developmental toxicity is one of the most difficult endpoints to assess, on account of the complexity, length and costs of experiments. Following the encouragement of QSAR (in silico) methods provided in the REACH itself, the CAESAR project has developed several models.

Results

Two QSAR models for developmental toxicity have been developed, using different statistical/mathematical methods. Both models performed well. The first makes a classification based on a random forest algorithm, while the second is based on an adaptive fuzzy partition algorithm. The first model has been implemented and inserted into the CAESAR on-line application, which is java-based software that allows everyone to freely use the models.

Conclusions

The CAESAR QSAR models have been developed with the aim to minimize false negatives in order to make them more usable for REACH. The CAESAR on-line application ensures that both industry and regulators can easily access and use the developmental toxicity model (as well as the models for the other four endpoints).

     

Hypergolic N,N‐Dimethylhydrazinium Ionic Liquids

N,N‐Dimethylhydrazinium dicyanamide and nitrocyanamide ionic liquids (ILs) were prepared by quaterization of N,N‐dimethylhydrazine with alkyl halides followed by metathesis reactions with silver dicyanamide or silver nitrocyanamide. The key physicochemical properties, such as melting point and decomposition temperatures, density, viscosity, heat of formation, detonation pressure and velocity, and specific impulse were measured/calculated. The impact of anions and alkyl‐substituted cations on these properties is demonstrated. Droplet tests with white‐fuming nitric acid (WFNA) as an oxidizer were utilized to show that the 14 new N,N‐dimethylhydrazinium salts are hypergolic with ignition delay (ID) times ranging from 22 to 1642 ms, thereby suggesting that some may have potential as bipropellants.     

Efficient Olefin Epoxidation by Robust Re4 Cluster‐Supported MnIII Complexes with Peracids: Evidence of Simultaneous Operation of Multiple Active Oxidant Species,MnVO,MnIVO,and MnIII?OOC(O)R

Two new tetranuclear chalcocyanide cluster complexes, [{Mn(saloph)H₂O}₄Re₄Q₄(CN)₁₂]?4 CH₃OH? 8 H₂O (saloph=N,N′‐o‐phenylenebis(salicylidenaminato), Q=Se ( 1 ‐Se), Te ( 2 ‐Te)), have been synthesized by the diffusion of a methanolic solution of [PPh₄]₄[Re₄Q₄(CN)₁₂] into a methanolic solution of [Mn(saloph)]⁺. The structure of 2 ‐Te has been determined by X‐ray crystallography. These rhenium cluster‐supported [Mn^III(saloph)] complexes have been found to efficiently catalyze a wide range of olefin epoxidations under mild experimental conditions in the presence of meta‐chloroperbenzoic acid (mCPBA). Olefin epoxidation by these catalysts is proposed to involve the multiple active oxidants Mn^V?O, Mn^IV?O, and Mn^III? OOC(O)R. Evidence in support of this interpretation has been derived from reactivity and Hammett studies, H₂¹⁸O‐exchange experiments, and the use of peroxyphenylacetic acid as a mechanistic probe. Moreover, it has been observed that the participation of Mn^V?O, Mn^IV?O, and Mn^III? OOC(O)R can be controlled by changing the substrate concentration. This mechanism provides the greatest congruity with related oxidation reactions that employ certain Mn complexes as catalysts.     

PEO-LiC104-SiO2-SCA体系电化学性能研究

选用硅烷偶联剂(SCA)对聚环氧乙烯(PEO)基固态聚合物电解质体系进行改性.通过XRD,DSC,SEM,FTIR,EIS 和拉伸性能测试等方法对材料进行了表征,考察了SCA对电解质电化学性能和力学性能的影响;对SCA的作用进行了分析.结果显示,SCA的加入显著降低了体系的结晶度,材料的电化学性能和力学性能得到了明显的改善.PEOB-LiC1Oa-5%SiO2-SCA体系室温电导率达到9.0×10-4S/cm,屈服强度达到2.04MPa(25℃).同时,SCA使电解质膜表面变得更为光滑、致密,这有利于降低与电极片间的接触阻抗.