小分子硫原子团簇正离子的结构稳定性

用分子图形软件设计出49种硫原子团簇Sn+(n=3～13)的结构,使用B3LYP密度泛函进行几何构型优化和振动频率计算,根据分子的总能量得出最稳定的同分异构体.在硫原子团簇正离子中,大部分原子为二配位成键.带有一、三配位的原子结构的总能量较高.部分最稳定硫原子团簇正离子的构型与最稳定的中性硫原子团簇的构型完全不同.     

小分子硫原子团簇的结构稳定性

用分子图形软件设计出68种硫原子团簇S_3～S_(13)的结构,使用B3LYP密度泛函进行几何构型优化和振动频率计算,排除了振动频率为负值的非局域极小点的结构,根据分子的总能量得出最稳定的同分异构体。在硫原子团簇中,除了部分原子采用一、三配位之外,大部分原子为二配位成键,带三配位的硫原子团簇的总能量较高,硫原子团簇难以生成高配位的笼状结构。从S_5开始链状结构能量高于环状,中性大分子硫原子团簇多呈链状结构。     

An Approach to Monocrowned Tiacalixarene

Thiacalixarenes are macrocycles comprising phenolic units connected in the ortho position by sulfur bridges instead of the methylene bridges of calixarenes.[1] When thiacalixarene was bridged with polyoxyethylene segments, thiacalixcrowns or crowned thiacalixarenes were constructed. Up to date, some thiacalix[4]biscrowns as well as a few thiacalix[4]monocrowns have been reported.     

Determination of antiferromagnetic exchange coupling in the tetrahedral thiolate-bridged diferrous complex [Fe2(SEt)6]2-

Protein-bound iron-sulfur clusters and their synthetic analogues are characterized by tetrahedral metal sites, multiple oxidation levels, and exchange coupling. The recent attainment of several all-ferrous protein clusters and the presence of sulfide- and thiolate-bridged sites in the all-ferrous state of the nitrogenase P-cluster provides an imperative for determination of exchange coupling between tetrahedral Fe(II) sites with sulfur bridges. The cluster in the previously reported compound (Et(4)N)(2)[Fe(2)(SEt)(6)] is centrosymmetric with distorted tetrahedral coordination and a planar Fe(2)(mu-SEt)(2) bridge unit. The compound is diamagnetic at 4.2 K, indicating antiferromagnetic coupling. The lower limit J > 80 cm(-)(1) (H = JS(1).S(2)) is obtained by M?ssbauer spectroscopy. Analysis of magnetic susceptibility data affords J = 165 +/- 15 cm(-)(1). It is noteworthy that the J value of the diferrous pair obtained here is comparable to the J values reported for the mixed-valence state of plant-type Fe(2)S(2) ferredoxins. The near temperature independence of the quadrupole splitting (DeltaE(Q) = 3.25 mm/s at 4.2 K and 3.20 mm/s at 180 K) indicates that no excited orbital states are appreciably populated at temperatures less than 300 K. The paramagnetism arises solely from thermal population of the S = 1 state of the spin ladder. This work provides the only measure of antiferromagnetic coupling by Fe(II) pairs in a tetrahedral sulfur environment.     

硫敏化中心中的银原子簇的增感作用

采用一定电位范围内的氧化还原缓冲液处理单分散立方溴化银乳剂颗粒表面上的硫敏化中心和由曝光生成的潜影中心,考察银原子簇的漂白和再生后的曝光响应曲线.实验结果再一次确认硫敏化中心中存在的银原子簇对硫敏化起重要作用,而且敏化效果也与银原子簇的含量有关.为此,提出硫敏化中心是由硫化银簇与银簇组成,它们在潜影形成的过程中各起不同的作用,但都有利于提高潜影的生成效率,因而共同产生敏化效应.     

Synthesis and characterization of oxygen and sulfur bridged aromatic macrocycles

The synthesis of nine 16–18–20–22 membered, oxygen and sulfur bridged aromatic macrocycles is reported, and reaction pathways to macrocycles formation are described. Molecular characterization of the nine compounds has been achieved by their mass spectra. Due to the cyclic nature of the compounds analyzed, the mass spectra are of particular interest. The 16–18-membered macrocycles, containing single oxygen and sulfur bridges, display very strong molecular ion intensities, while the 20–22-membered macrocycles, containing double bridges, show lower stability to electron-impact, and the molecular ion intensities are lower. Some of the salient features of the electron fragmentation processes are briefly discussed in the text.     

Formation, detection, and stability studies of neutral vanadium sulfide clusters

Neutral vanadium sulfide clusters are generated by the reaction of seeded hydrogen sulfide in a helium carrier gas with laser ablated vanadium metal within a supersonic nozzle. The exiting clusters are expanded into a vacuum in a molecular beam and are ionized by both ultraviolet (UV) and vacuum UV (VUV) laser radiation. The generated ions are detected by a time of flight mass spectrometer. With single photon ionization (SPI) employing VUV (118 nm) radiation, sulfur rich clusters (V(m)S(n), n>m+1) and hydrogen containing clusters (V(m)S(n)H(x), x>0) are observed. With multiphoton ionization (MPI) through nanosecond UV (193 nm) radiation, these sulfur rich and hydrogen containing clusters cannot be observed, indicating severe fragmentation generated by MPI and the importance of SPI in determining the neutral vanadium sulfide cluster distribution. With MPI through femtosecond UV (226 nm) radiation, a few sulfur rich and hydrogen containing clusters are detected, but most clusters observed by SPI are still undetected even by femtosecond MPI. Density functional theory calculations are applied to optimize energies and structures of the clusters with m=1-3 and n=0-7. The experimental results are well interpreted based on the calculations. The calculated and experimental results for vanadium sulfides are compared with those of vanadium oxides in literature.     

A density functional study for the isomers of anionic sulfur clusters Sn− (n=3–20)

The signals of anionic sulfur clusters are intense in the mass spectrum of sulfur clusters generated in direct laser vaporization. We have acquired numerous isomers of sulfur clusters by means of the B3LYP DFT method. According to total energies, the most stable S_n⁻ (n=3–13) isomers are predicted. The helical S_n (n=14–20) structures are also calculated. Most of the anionic clusters are with chain configurations; the ring clusters with threefold atom(s) are higher in total energy. The most stable forms of isomers, from S₉⁻ to S₁₃⁻, show helical configurations that are completely different from those of the corresponding neutral and cationic clusters.     

Persulfuration of phosphinines: Synthesis and X-ray crystal structure analysis of a P2S3 derivative

The reaction of 4,5-dimethyl-2-phenylphosphinine with sulfur in boiling benzene in the presence of N-methylimidazole as a catalyst first yields a P-sulfide. This monosulfide further reacts with sulfur to give a diphosphinine trisulfide and a diphosphinine tetrasulfide. The X-ray crystal structure analysis of the trisulfide has been carried out. The two head-to-tail 1,6-dihydrophosphinine rings are connected by P S C and P C links, thus forming a central 1,2,4-thiadiphospholane heterocycle. The P C bridge is weak [1.881(3) Å] and sulfur can insert into it to give the symmetrical tetrasulfide with two P S C bridges.     

硫原子团簇负离子的螺旋结构

在使用B3LYP密度泛函进行几何构型优化和振动频率计算得到的硫原子团簇负离子的结构中,分子的总能量最低的S9- 到 S13-的同分异构体呈螺旋状构型。另外也计算了螺旋状的Sn- (n = 14~20)的结构。大多数的的硫负离子是链状结构,这与相应中性硫原子团簇的环状构型完全不同。     

Theoretical Study on the Catalytic Activity and Sulfur Resistibility of Amorphous Alloy Ni-B-P

In the present paper,one hundred cluster models NinBP (n=1～6) have been designed and studied by density functional theory (DFT) to get an insight into the local structure,catalytic properties and sulfur resistibility of amorphous alloy Ni-B-P. The configurations in triplet state are found more stable than those in the singlet state. It is found that as the content of Ni in the clusters increases,the value of Fermi level in clusters fluctuated,which shows that the content of Ni can influence the Fermi level to a certain extent. Based on the Fermi level and DOS,we consider the activity of catalyst in hydrogenation reaction is the best in cluster Ni3BP. On the basis of the charge of clusters NinBP (n=1～6),we conclude the amorphous alloy Ni-B-P with high Ni content has better sulfur resistibility and the best hydrogenation activity,strong sulfur resistibility appears in clusters Ni3BP,and the amorphous alloy Ni60B20P20 with similar proportion is expected to prepare in the future.     

AgnSm^±和AunSm^±的激光产生与质谱研究

以高能量密度的脉冲激光束在高真空中直接溅射银(金)粉与硫的混合物, 产生了丰富的银-硫和金-硫二元原子族正负离子, 记录了它们的飞行时间质谱。通过对这些簇离子的组成与分布的分析, 发现了它们的一些结构规律。银硫簇离子以离子键为主, Ag2S是它们的主要结构单元, 其中Ag11S5^+和Ag9S5^-特别稳定; 金硫簇离子基本上是共价结构, 金原子间相互成键, 构成簇离子的核, 硫原子则仅与核表面的金原子配位, 其中Ag6S14^+, Au5S6^-的稳定性比较突出。     

S-alkylation of thiacalixarenes: a long-neglected possibility in the calixarene family

Despite the high nucleophilicity of sulfur atoms, thiacalixarenes have been alkylated only on oxygen atoms thus far. Using strong alkylating agents (triflates, trialkyloxonium salts), the substitution of the sulfur bridges has been successfully accomplished. The corresponding sulfonium salts of thiacalix[4]arene are formed regio- and stereoselectively as a completely new type of substitution pattern in thiacalixarene chemistry. These compounds possess interesting conformational behavior and could be used as unusual alkylating agents with uncommon selectivity.     

卤化银成像体系中的硫增感

从感光乳剂硫增感敏化中心的形成和作用机理等方面对硫增感过程进行了综合叙述,并对硫敏化中心的分布、增感条件、增感中心的性质、增感团簇的研究、新型的硫增感手段等方面的理论进展也作了讨论.     

电镜法对硫敏化中心的直接观察

敏化中心的形成是Ag₂S的聚集过程, 一般包括两步^[1]. 在第一步中, 增感剂中的硫离子与银离子在AgX晶体表面生成Ag₂S分子, 然后, 多个Ag₂S分子接合(coalescence)形成敏化中心.     

Mild preparation of functionalized [2.2]paracyclophanes via the Pummerer rearrangement

[2.2]Paracyclophanes, incorporating functional groups in the aliphatic bridges, suitable for elimination to give [2.2]paracyclophanedienes, are synthesized through a novel approach. It relies on a double Pummerer rearrangement on dithiacyclophane precursors, followed by ring contraction through a photochemical sulfur extrusion, and it is compatible with aryl moieties possessing very different electronic properties.     

Assembly of [Mn(II)2Mn(III)2] S = 9 clusters via azido bridges: a new single-chain magnet

In the present work, we report a new manganese single-chain magnet built from tetranuclear Mn(II)(2)Mn(III)(2) mixed-valence units linked by end-on azido and oximato bridges. All of the intra- and intercluster interactions involve end-on azido bridges, resulting in one ferromagnetic chain of ferromagnetic clusters with local ground state S = 9.     

Bridges between trinuclear metal clusters

Our research on trinuclear Os and Ru carbonyl clusters linkedvia inorganic and organic bridges is reviewed in the context of the nature of the interaction between the linked clusters. The component clusters can behave as essentially independent entities (TYPE A). The component trinuclear species may fuse to form new higher nuclearity clusters in which the indentities of the components are lost (TYPE B). Alternatively, the cluster units retain their identities but for electronic reasons there is long-range metal-metal bonding between them (TYPE C).     

Study on absolute configurations of α/α′ chiral carbons of thiodiketopiperazines by experimental and calculated circular dichroism spectra

We report here new investigations of the CD of TDKPs (including new structural types). Some unprecedented rules between ACs and CD spectra are deduced from the studies of experimental and calculated CD of them as follows: (1) the CD band around 270 nm could be applied to determine the ACs of the chiral carbons at α/α′ positions in TDKPs. (2) The intensities of CE around 270 nm followed the decreasing trend: disulfide bridges >S-methyl groups> single sulfur bridges. (3) While the sulfur atom attached to the α position of the saturated cyclohexanone in the axial bond form, the CE in the 300 nm can be used to determine the AC of the chiral carbon at the α position of the six-membered ring. (4) The apparent violation of the skewed diene rule in 18 may be due to a strong interaction of the diene, and the S-methyl group and sulfur bridge.     

Theoretical Study of Small Water Clusters of Sulfur Dioxide

The intermolecular clusters of sulfur dioxide with water, SO2(H2O)n (n = 2～5), are studied by using B3LYP density functional theory and MP2 ab initio methods along with the large basis sets (6-311++G(d,p) and aug-cc-pVDZ). The equilibrium geometries, intermolecular binding energies, and anharmonic frequencies of the clusters are calculated and compared with those of pure water clusters and available experiments. SO2 tends to form cyclic hydrogen-bonded complexes with two or three water molecules. In the larger clusters, however, water molecules begin to retain the structure of pure water clusters and segregate from SO2. Infrared absorption assignments for the small clusters are discussed to resolve a possible incorrect assignment in a recent spectroscopic experiment on the clusters.