De Novo Construction of Catenanes with Dissymmetric Cages by Space‐Discriminative Post‐Assembly Modification

Considerable efforts have been made to increase the topological complexity of mechanically interlocked molecules over the years. Three‐dimensional catenated structures composed of two or several (usually symmetrical) cages are one representative example. However, owing to the lack of an efficient universal synthetic strategy, interlocked structures made up of dissymmetric cages are relatively rare. Since the space volume of the inner cavity of an interlocked structure is smaller than that outside it, we developed a novel synthetic approach with the voluminous reductant NaBH(OAc)₃ that discriminates this space difference, and therefore selectively reduces the outer surface of a catenated dimer composed of two symmetric cages, thus yielding the corresponding catenane with dissymmetric cages. Insight into the template effect that facilitates the catenation of cages was provided by computational and experimental techniques.     

Macrocyclic Metal Complexes Bearing Rigid Polyaromatic Ligands: Synthesis and Catalytic Activity

We synthesised palladium and platinum complexes possessing cyclic and acyclic pincer‐type polyaromatic ligands and investigated their structural effect on the catalysis. The pincer‐type bis(6‐arylpyridin‐2‐yl)benzene skeleton was constructed via Kröhnke pyridine synthesis under transition metal‐free conditions on gram‐scale quantity. Ligand structure significantly influenced catalytic activity toward the platinum‐catalysed hydrosilylation of diphenyl acetylenes, despite the ligand‐independence of the conformations and electronic properties of these complexes.     

A novel three‐dimensional tetranuclear CoII coordination polymer with water hexamers based on the V‐shaped tetracarboxylate ligand 4‐(2,4‐dicarboxylatophenoxy)phthalate

A new coordination polymer (CP), namely, poly[[diaquatris[μ₂‐1,4‐bis(1H‐imidazol‐1‐yl)benzene]bis[μ₆‐4‐(2,4‐dicarboxylatophenoxy)phthalato]tetracobalt(II)] hexahydrate], {[Co₄(C₁₆H₆O₉)₂(C₁₂H₁₀N₄)₃(H₂O)₂]·6H₂O}_n, has been synthesized by solvothermal reaction. The CP was fully characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, and powder and single‐crystal X‐ray diffraction. It presents a three‐dimensional (3D) structure based on tetranuclear Co^II secondary building units (SBUs) with a tfz‐d net and point symbol (4³)₂(4⁶·6¹⁸·8⁴). The 4‐(2,4‐dicarboxyphenoxy)phthalic acid (H₄dcppa) ligands are completely deprotonated and link {Co₄(COO)₄}^4? SBUs into two‐dimensional (2D) layers. Furthermore, adjacent layers are connected by 1,4‐bis(1H‐imidazol‐1‐yl)benzene (bib) ligands, giving rise to a 3D supramolecular architecture. Interestingly, there are numerous elliptical cavities in the CP where isolated unique discrete hexameric water clusters have been observed. The results of thermogravimetric and magnetic analyses are described in detail.     

A 3D Porous Metal Organic Framework Based on Infinite 1D Nickel(II) Chains with Rutile Topology Displaying Open Metal Sites

The reaction of Ni^II with a tetra‐benzoate pyrene ligand produces a 3D porous framework based on infinite 1D Ni^II chains. The Ni^II–O connectivity and the formation of a hydroxo‐bridge (μ₃‐OH) responsible for the connection of the central Ni^II atoms within the 1D Ni^II–(μ₃‐OH)₂–Ni^II chains can be straightforwardly compared with the Ti^IV–O–Ti^IV connectivity seen in TiO₂. The arrangement of the TBAPy ligand around the 1D rutile‐based chains leads in the generation of a porous framework with two distinct types of pores; based on the chemistries of these two types of pores, one can be labelled as hydrophobic and the other as hydrophilic. The use of different activation methods results in the generation of either a porous framework free of guest molecules or a completely solvent‐free material, in which the terminal H₂O molecules bound to Ni^II were removed, leading thus to a framework with open Ni^II sites. CO₂ isotherms collected on both frameworks at 195 K and one barshowed type I isotherms characteristic of microporous materials (BET surface areas for: guest‐free framework: 257(3) m² · g^–1; solvent‐free framework: 362(2) m² · g^–1). The affinity of both networks at zero coverage for both CO₂ and CH₄ was found to be greater when the unsaturated Ni^II sites are available within the void space.     

以D-樟脑酸与1,4-二（咪唑-1-基）丁烷为配体构筑的两个配位聚合物的结构与磁性

水热合成了2个以D-樟脑酸(D-H2cam)与1,4-二(咪唑-1-基)丁烷(1,4-bimb)为配体的配位聚合物:[Co(D-cam)(1,4-bimb)]n·4nH2O(1)和[Ni(D-cam)(1,4-bimb)]n(2)。通过X-射线单晶衍射,元素分析,红外光谱,XRD分析,热重,和磁性分析对其结构进行了表征。测定了这两个聚合物的磁性。结构分析表明,1为P2空间群,其链状结构由氢键作用连接形成二维结构;2为Pna21空间群,呈四重穿插的dia网络结构。     

Synthesis,Crystal Structure and Properties of Na2MnO2

Na₂MnO₂ was prepared via the azide/nitrate route. Stoichiometric mixtures of the precursors (Mn₂O₃, NaN₃ and NaNO₃) were heated in an appropriate regime up to 390 °C and annealed at this temperature for 20 h, in specially designed silver containers. As the most prominent feature, the crystal structure of Na₂MnO₂ (C2/c, Z = 12, a = 12.5026(9), b = 12.1006(9), c = 6.0939(4) Å, β = 117.94(0)°, 1556 independent reflections, R₁ = 3.83 % (all data)) forms a three dimensional framework polyanion of corner sharing MnO₄‐tetrahedra. The connectivity pattern of the tetrahedral building units corresponds to the moganite structure, a rare SiO₂ modification. According to measurements of the magnetic susceptibility in the temperature range from 2 to 750 K, Na₂MnO₂ shows antiferromagnetic ordering below 250 K. Evaluation of the high temperature data employing the Curie‐Weiss law revealed a magnetic moment of μ_eff = 5.93 μ_B, confirming the presence of divalent manganese.     

Some properties for the largest component of random geometric graphs with applications in sensor networks

In this paper we consider the standard Poisson Boolean model of random geometric graphs G（Hλ,s; 1） in Rd and study the properties of the order of the largest component L1 （G（Hλ,s; 1）） . We prove that ElL1 （G（Hλ,s; 1））] is smooth with respect to A, and is derivable with respect to s. Also, we give the expression of these derivatives. These studies provide some new methods for the theory of the largest component of finite random geometric graphs （not asymptotic graphs as s - co） in the high dimensional space （d 〉 2）. Moreover, we investigate the convergence rate of E[L1（G（Hλ,s; 1））]. These results have significance for theory development of random geometric graphs and its practical application. Using our theories, we construct and solve a new optimal energy-efficient topology control model of wireless sensor networks, which has the significance of theoretical foundation and guidance for the design of network layout.     

Rhorix: An interface between quantum chemical topology and the 3D graphics program blender

Chemical research is assisted by the creation of visual representations that map concepts (such as atoms and bonds) to 3D objects. These concepts are rooted in chemical theory that predates routine solution of the Schrödinger equation for systems of interesting size. The method of Quantum Chemical Topology (QCT) provides an alternative, parameter‐free means to understand chemical phenomena directly from quantum mechanical principles. Representation of the topological elements of QCT has lagged behind the best tools available. Here, we describe a general abstraction (and corresponding file format) that permits the definition of mappings between topological objects and their 3D representations. Possible mappings are discussed and a canonical example is suggested, which has been implemented as a Python “Add‐On” named Rhorix for the state‐of‐the‐art 3D modeling program Blender. This allows chemists to use modern drawing tools and artists to access QCT data in a familiar context. A number of examples are discussed. © 2017 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.     

Chiral symmetry breaking and vacuum structure in QCD

The solution of the axial U(1) problem, the role of the topology of the gauge group in forcing the breaking of axial symmetry in any irreducible representation of the observable algebra and the θ vacua structure are revisited in the temporal gauge with attention to the mathematical consistency of the derivations. Both realizations with strong and weak Gauss law are discussed; the control of the general mechanisms and structures is obtained on the basis of the localization of the (large) gauge transformations and the local generation of the chiral symmetry. The Schwinger model in the temporal gauge exactly reproduces the general results.