Cluster Chemistry

Metal cluster chemistry is one of the most rapidly developing areas of inorganic and organometallic chemistry. Prior to 1960 only a few metal clusters were well characterized. However, shortly after the early development of boron cluster chemistry, the field of metal cluster chemistry began to grow at a very rapid rate and a structural and a qualitative theoretical understanding of clusters came quickly. Analyzed here is the chemistry and the general significance of clusters with particular emphasis on the cluster research within my group. The importance of coordinately unsaturated, very reactive metal clusters is the major subject of discussion.     

Hydroxo-Lanthanide Cluster Organic Framework Built by Hexanuclear Cluster Units

A novel hydroxo-lanthanide cluster organic framework, Sm₃L₈(μ ₃-OH)(H₂O)·H₂O (1), derived from the 4-pyridin-4-ylbenzoic acid (HL) has been hydrothermally made and structurally characterized by single crystal X-ray diffraction. Structure analysis shows the hexanuclear Sm₆ cluster unit is composed of inorganic tetranuclear hydroxo [Sm₄(OH)₂]¹⁰⁺ (Sm₄) cluster and dimeric [Sm₂(COO)₄]²⁺ (Sm₂) core. The Sm₆ cluster units are connected by L ligands to form a 2D Ln-based cluster organic framework. From the topological point of view, the layer architecture can be described as 4-connected sql net. Furthermore, the elemental analysis, PXRD, IR and TGA are also studied.     

Mean Gas Cluster Size Determination from Cluster Beam Cross-Section

This paper describes the simple experimental method of size determination of gas clusters in molecular beams formed from supersonic jets. Mean cluster size N is calculated from broadening of the transverse profile of beam intensity at a fixed distance behind the skimmer. The described method allows determining the mean sizes of the clusters of any pure gases. It does not require the building of some special models, or determination of empirical constants. Due to the high intensity of the supersonic beams, the measurements do not require any complex highly sensitive equipment. The effectiveness of the present method is validated by measurements in a cluster beams of test gases (easily condensable CO₂, Ar, and weakly condensable N₂) and the beam of C₂H₄ (ethylene), formed from a supersonic jet behind conical nozzles. The certainty of measured characteristics is confirmed by the results of numerical simulations. By using the described method the mean cluster sizes from 50 to 2000 molecules per cluster were determined. The correctness of the obtained cluster sizes of CO₂ and Ar is proved by comparison with results of other authors, obtained by other experimental methods, and estimations according to the empirical correlations using condensation scaling parameter Г^*.     

Tetraplatinum Cluster Complexes

The tetranuclear platinum cluster complexes [Pt₄(-CO)₃(-dppm)₃(PPh₃)]²⁺ and [Pt₄(-H)(-CO)₂(-dppm)₃(PPh₃)]⁺ have been prepared by cluster expansion. They have butterfly structures and are fluxional.     

树形分子保护下铜原子簇的制备

纳米粒子由于其独特的光、电、磁和热学性质,在基础理论和应用研究方面都引起了广泛的关注.其中过渡金属纳米粒子因在催化、磁流体等领域的应用前景而引起人们浓厚的兴趣.过渡金属纳米粒子的性质不仅与粒子的大小有关,还受其形状、均匀性、团聚状况和氧化态的影响.因此制备大小和形状可控的原子簇一直是纳米材料科学中富有挑战性的课题.自从1985年Tomalia等[1]首次用发散法合成聚酰胺-胺树形分子以来,树形分子就因其独特的结构特点而成为材料学领域研究的热点之一.     

Cluster analysis of molecular conformations

We describe a method for locating clusters of geometrically similar conformers in ensembles of chemical conformations. We first calculate the pairwise interconformational distance matrix in either torsional or Cartesian space and then use an agglomerative, single-link clustering method to define a hierarchy of clusterings in the same space. Especially good clusterings are distinguished by high values of the separation ratio: the ratio of the shortest intercluster distance to the characteristic threshold distance defining the clustering. We also discuss other statistics. The method has been embodied in a program called XCluster, which can display the distance matrix, the hierarchy of clusterings, and the clustering statistics in a variety of formats. XCluster can also write out the clustered conformations for subsequent or simultaneous viewing with a molecular visualization program. We demonstrate the sorts of insight that this approach affords with examples obtained from conformational search and molecular dynamics procedures. © 1994 by John Wiley & Sons, Inc.     

Cluster expansion of the wavefunction

Numerical examples illustrate the SAC and SAC-CI results for correlatioin energies compared to those from full CI calculations of Bauschlicher and Taylor.     

Cluster Organic Framework Based on Er3 and Cu5 Cluster Units

A novel cluster organic framework, Er₃Cu₅I₄L₁₀(H₂O) (1, L = 4-pyridin-3-yl-benzonate), has been hydrothermally made and structurally characterized by single crystal X-ray diffraction. Structure analysis shows [Er₃(COO)₆]³⁺ (Er₃) clusters are linked by carboxylate groups generating one dimensional wave-like chain, which further extended by Cu₅I₄ ⁺ (Cu₅) clusters into three dimensional heterometallic cluster organic framework. From the perspective of topology, such framework defines a new (7,9)-connected net, considering Er₃ and Cu₅ cores as the nodes. Furthermore, the elemental analysis, powder X-ray diffraction, infrared spectra and thermogravimetric analysis are also studied.     

From Cluster to Cluster: Structural Transformation Reactions Among Tungsten Chloride Clusters

Reactions between tungsten halides are discussed along the series of compounds WCl₆ → WCl₄ → W₆Cl₁₂ ↔ W₆Cl₁₈ → [W₆CCl₁₈]ⁿ⁻ ← [W₃Cl₁₃]^u−, focusing on the two closely related tungsten chloride compounds whose structures compromise the well-known octahedro W₆Cl₁₈ cluster and the carbon-centered triprismo W₆CCl₁₈ cluster. Both clusters can be regarded as being built by merging two trigonal [W₃Cl₁₃]^u− units in different ways. Syntheses, structural transformation reactions, and concepts regarding electronic structures are reported.     

Cluster ruthenium hydrogenation catalysts

Tetraruthenium dodecacarbonyl tetrahydride and some of its phosphine-substituted derivatives have been tested as homogeneous hydrogenation catalysts. The hydrogenation of cyclohexanone in the presence of H₄Ru₄(CO)₁₂ is first order with respect to the catalyst concentration, the substrate concentration and the partial pressure of hydrogen. The ruthenium cluster is recovered unchanged at the end of the reaction.     

水分子簇的研究进展

水分子簇结构与功能的探索已引起科学界的广泛关注并逐渐成为簇科学研究领域中的一个热点。本文综述了近年来水分子簇间作用力研究的进展、内容和方法并加以比较, 重点介绍了远红外振转隧道光谱法, 简述了超冷水的分子结构特征, 并对该领域的研究前景作了展望。     

中药黄芩及其混伪品的模糊聚类分析

采用模糊聚类分析法对黄芩及其混伪品进行了聚类分析,为中药材的质量鉴定提供了新方法。     

硼烷簇合物的结构规则

从超额电子数出发，提出了1种稠合型硼烷的结构规则，讨论了各种规则间的关系。     

Cluster distance geometry of polypeptide chains

Distance geometry has been a broadly useful tool for dealing with conformational calculations. Customarily each atom is represented as a point, constraints on the distances between some atoms are obtained from experimental or theoretical sources, and then a random sampling of conformations can be calculated that are consistent with the constraints. Although these methods can be applied to small proteins having on the order of 1000 atoms, for some purposes it is advantageous to view the problem at lower resolution. Here distance geometry is generalized to deal with distances between sets of points. In the end, much of the same techniques produce a sampling of different configurations of these sets of points subject to distance constraints, but now the radii of gyration of the different sets play an important role. A simple example is given of how the packing constraints for polypeptide chains combine with loose distance constraints to give good calculated protein conformers at a very low resolution.