On the origin of ferromagnetism in oximato-based [Mn3O]7+ triangles

DFT calculations reveal the unusual ferromagnetic exchange observed in an oxo-centered Mn(III) triangle may originate from a combination of the 'non-planarity' of the bridging oxime ligands and the non-parallel alignment of the Jahn-Teller axes.     

Studies of an Fe9 tridiminished icosahedron

The synthesis and structural characterization of a nonanuclear FeIII cage complex is reported. The nine iron centers in [Fe9(mu3-O)4(O3PPh)3(O2CCMe3)13] lie on the vertices of an incomplete icosahedron, with the P atoms of triphenylphosphonate at the other three vertices. The paramagnetic core therefore describes a tridiminished icosahedron. Magnetic studies suggest an S=1/2 ground state for the molecule. Analysis of exchange paths and the susceptibility data point to the interpretation that the cluster can be divided into two nearly decoupled sections: an {Fe6O3} section, with an S=0 ground state, in which three oxo-centered triangles bound a central triangle that is not oxo-centered; and an {Fe3O} triangle with S=1/2. The analysis of the susceptibility data leads to a Heisenberg model based on three significant antiferromagnetic exchange interactions, with values of 173.7 cm-1 in the {Fe3O} triangle, and 30.9 and 19.1 cm-1 within the {Fe6O3} section, while the exchange between them is <1 cm-1. With these assignments, the theoretical low-temperature differential susceptibility is also in very good agreement with measurements up to 50 T. Magnetic measurements in the milli-kelvin range reveal striking hysteresis loops and magnetization reversals associated with a Landau-Zener-Stückelberg (LZS) transition as enhanced by the occurrence of a phonon bottleneck.     

SCF non-additivity of the interaction energy in the neon trimer

The three-body non-additivity of the interaction energy for the equilateral triangle configuration of the Ne₃ system has been calculated, using the counterpoise method within the SCF approach. The induction-type non-additivity has been estimated and compared with the first-order exchange one.     

三核苯甲酸铁配合物［Fe_3O（OBZ）_6（H_2O）_3］（NO_3）（a

合成了三核苯甲酸铁配合物［Ｆｅ３Ｏ（ＯＢＺ）６（Ｈ２Ｏ）３］（ＮＯ３）（ａｃｅｔｏｎｅ）５．测定了其晶体结构．其中三个铁形成等边三角形结构．配合物的变温磁化率表明，分子内三个铁之间有弱的反铁磁性交换作用，Ｊ＝－３３．１８ｃｍ－１．分子之间则有更弱的反铁磁性交换作用，ｚＪ＇＝－１．１４ｃｍ－１．     

Synthesis and studies of a trinuclear Mn(II) carboxylate complex

We report a carboxylate triangle consisting of three manganese(II) centres which is made from manganese(II) carbonate and pivalic acid. The magnetic exchange within the triangle is extremely weak, and antiferromagnetic. Several models have been used to fit the magnetic data, and the best fit uses two weak antiferromagnetic coupling constants of J(1)=-0.588 cm(-1) and J(2)=-0.855 cm(-1). Exchange interactions between the metal centres has been calculated using DFT adopting all the three possible Heisenberg models for a trinuclear system and the results are compared with experimental values. Spin density distribution is used to analyse the nature of the coupling between the metal centres. EPR spectroscopy has been used to explore the nature of the ground state. Recrystallisation of the trinuclear compound from MeCN gives a polymer, while oxidation in air leads to a known compound--an edge-sharing bitetrahedral (MnIII2MnII4) cage.     

Many-orbital cluster expansion for the exchange-repulsion nonadditivity in the interaction of rare gas atoms. The neon trimer

Nonadditivity of the exchange repulsion for three neon atoms in the equilateral triangle configuration has been calculated in the first-order of the symmetry adapted perturbation theory. The relative nonadditive contribution to the first-order interaction energy has been found to be about twice as small as in the helium trimer. The many-orbital cluster partition of the exchange nonadditivity has been derived. It has been found that in the region of the van der Waals minimum about 95% of the exchange nonadditivity originates from the interaction of the L-shell electrons only. The five-orbital terms as well as terms of an order-higher than S³ have been found to be negligible. Approximate formulae for evaluation of the exchange repulsion nonadditivity has been proposed and discussed.This work was partly supported by the Polish Academy of Sciences within the project MR.I.9.     

Low temperature EPR spectra of the mesoscopic cluster V15: the role of antisymmetric exchange

The low temperature EPR spectra of the unique nanometer-scale molecular magnet V(15) are analyzed within the three-spin model preserving trigonal symmetry. The Hamiltonian includes isotropic and antisymmetric (AS) exchange interactions introduced by Dzyaloshinsky (Zh. Eksp. Teor. Fiz. 32, 1547 (1957) [Sov. Phys. JETP 5, 1259 (1957)]) and [Moria Phys. Rev. 120, 91 (1960)]. With the aid of pseudoangular momentum representation the exact selection rules for the EPR transitions are deduced. AS exchange in the frustrated triangular system gives rise to a first order zero-field splitting of two low lying spin doublets and to a second order splitting of the excited quadruplet. This leads to a peculiar series of strong intramultiplet transitions and weak intermultiplet transitions. We show that the intramultiplet transitions are allowed only when the vector of the AS exchange is normal to the plane of vanadium triangle, but the series of weak intermultiplet transitions are a consequence of the in-plane part of the AS exchange. We have revealed a special temperature dependence of the EPR pattern with a peculiar shape of the full spectrum. Experimental data on high-frequency EPR of V15 at ultralow temperature are discussed.     

Studies on the magnetic property of μ_3-oxotriiron(Ⅲ) complex [Fe_30(OBz)_6(CH30H)_3](NO_3)(CH_3OH)_2 (HOBz=Benzoic acid)

The magnetic property of u3-oxotriiron(III) complex [Fe3O(OBz)6(CH3OH)3](NO3)-(CH3OH)2 (HOBz=benzoic acid) has been studied. We use isosceles triangle model and molecular field correction to fit the experimental magnetic susceptibility data. It shows that an intramolecular antiferromagnetic exchange interaction occurs with J=-31.27 cm-1, J'=-27.26 cm-1, and a weaker intermolecular antiferromagnetic exchange interaction occurs with zJ'=-3.76 cm-1. We give the d5-d5-d5 energy level diagram of triiron(III) complex as a function of J'/J. From the diagram we can get the total spin ST of the complex as 1/2 in the ground state.     

Structural stability and electronic state of transition metal trimers

Ground state geometries were searched for transition metal trimers Sc3, Y3, La3, Lu3, Ti3, Zr3, and Hf3 by density functional methods. For all the studied trimers, our calculation indicates that the ground state geometries are either equilateral triangle (Zr3 and Hf3) or near equilateral triangle (Ti3, Sc3, Y3, La3, and Lu3). For rare earth trimers Sc3, Y3, La3, and Lu3, isosceles triangle (near equilateral triangle) at quartet state is the ground state. Isosceles triangle at doublet state is the competitive candidate for the ground state. For Zr3 and Hf3, equilateral triangle at singlet state is the most stable. For Ti3, isosceles triangle (near equilateral triangle) at quintet state gives the ground state. For Sc3, Zr3, and Hf3, where experimental results are available, the predicted geometries are in agreement with experiment in which the ground state is equilateral triangle (Zr3) or fluxional (Sc3 and Hf3). For Y3, the calculated geometry is in agreement with experimental observation and previous theoretical study that Y3 is a bent molecule for the ground state. For La3, our calculation is in excellent agreement with previous theoretical study based on density functional methods.     

三核苯甲酸铁配合物[Fe3O(OBZ)6(H2O)3](NO3)(acetone)5(OBZ-=苯甲酸根)的结构和磁性

合成了三核苯甲酸铁配合物［Ｆｅ３Ｏ（ＯＢＺ）６（Ｈ２Ｏ）３］（ＮＯ３）（ａｃｅｔｏｎｅ）５。测定了其晶体结构，其中三个铁形成等边三角形结构。配合物的变温磁化率表明，分子内三个铁之间有弱的反应磁性交换作用，Ｊ＝－３３．１８ｃｍ＾－１。分子之间则有更弱的反铁磁性交换作用，ＺＪ＾＇＝－１．１４ｃｍ＾－１。     

The structure and magnetic properties of μ3-oxotriiron(III) complex [Fe3O(OBz)6(CH3OH)3](NO3)(CH3OH)2

A new μ₃-O triiron(III) complex [Fe₃O(OBz)₆(CH₃OH)₃](NO₃)(CH₃OH)₂ (HOBZ = benzoic acid) has been synthesized, its structure has been determined and variable temperature magnetic susceptility has also been measured. In the molecule, three iron atoms formed an equilateral triangle with μ₃-O in center. The fitting to the magnetic susceptibility showed that an intramolecular antiferromagnetic exchange interaction occurred between iron atoms with J=-25.51 cm^?1, and a weaker intermolecular autiferromagnetic exchange interaction occurred with zJ' = ?2.30 cm^?1.     

Spontaneous and catalytic fusion of supramolecules

Using principles of completive and integrative self-sorting, a clean supramolecule-to-supramolecule transformation is realised that involves fusion of a 3-component rectangle and a 2-component equilateral triangle into a 5-component scalene triangle. While the spontaneous process takes 15 h at 25 °C, the catalytic transformation is completed within 1 h.     

苯甲醛肟偶极互变反应的理论研究

研究了苯甲醛肟Z构型和E构型两种异构体与相应偶极体的3条互变反应途径:(1)单分子内质子转移反应,质子由肟羟基转移至邻位的氮上,过渡态为三角形结构,反应能垒较高;(2)二聚体内的质子互换反应,质子分别从一个肟羟基转移到另一个肟的氮上,过渡态为六元环结构,能垒较低,理论反应速度较大,但平衡常数较小;(3)肟羟基与甲醇的质子互换反应,过渡态具有五元环结构,能垒和反应速度介于上述两者之间.结果表明,在3条反应途径上,Z构型和E构型均有类似的过渡态,Z构型有利于偶极体存在.在室温下主要通过二聚体内质子交换进行互变反应,实际体系中由于偶极体不断被消耗,反应可以持续进行.     

Nonadditivity and the stability of Ag3. A multireference configuration interaction study

Variational (?30 000 determinants) and perturbational (?3.5 million determinants) Localized Multireference Configuration Interaction (LMRCI) calculations includingf polarization functions are made to study the role played by the three-body terms in the stabilization energy of three selected geometries of the silver trimer: linear, equilateral and a Jahn-Teller obtuse triangle conformation. A comparative analysis of the relative stability of these geometries is done through a many-body decomposition of the interaction energy. Like in Cu₃, the most symmetrical arrangement (i.e. an equilateral triangle) is found to be less stable than the obtuse triangle because it has the highest three-body repulsion energy. The absolute minimum is the obtuse triangle having a Jahn-Teller stabilization energy of 328 cm^?1. Unlike Cu₃, the linear geometry is found to be less stable than the equilateral by 1282cm^?1. Results show again the importance of three-body terms in the total interaction energy of these trimers.     

Imaging of the structure of the argon and neon dimer, trimer, and tetramer

We Coulomb explode argon and neon dimers, trimers, and tetramers by multiple ionization in an ultrashort 800 nm laser pulse. By measuring all momentum vectors of the singly charged ions in coincidence, we determine the ground state nuclear wave function of the dimer, trimer, and tetramer. Furthermore we retrieve the bond angles of the trimer in position space by applying a classical numerical simulation. For the argon and neon trimer, we find a structure close to the equilateral triangle. The width of the distribution around the equilateral triangle is considerably wider for neon than for argon.     

Functionalizing Designer DNA Crystals with a Triple‐Helical Veneer

DNA is a very useful molecule for the programmed self‐assembly of 2D and 3D nanoscale objects. 1 The design of these structures exploits Watson–Crick hybridization and strand exchange to stitch linear duplexes into finite assemblies. 2 – 4 The dimensions of these complexes can be increased by over five orders of magnitude through self‐assembly of cohesive single‐stranded segments (sticky ends). 5 , 6 Methods that exploit the sequence addressability of DNA nanostructures will enable the programmable positioning of components in 2D and 3D space, offering applications such as the organization of nanoelectronics, 7 the direction of biological cascades, 8 and the structure determination of periodically positioned molecules by X‐ray diffraction. 9 To this end we present a macroscopic 3D crystal based on the 3‐fold rotationally symmetric tensegrity triangle 3 , 6 that can be functionalized by a triplex‐forming oligonucleotide on each of its helical edges.     

Contributions to the on-line method for the extraction and isolation of pesticide residues and environmental chemicals

Summary The principle of the on-line method is presented by the Gibbs triangle. It can be shown that in addition to the straight sequential or simultaneous working sequences also any combination of both can be used. Altogether, six working sequences are practicable with the on-line technique. Finally, the working sequences of two different online extraction procedures are discussed and presented by the Gibbs triangle.

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BeitrÄge zur on-line Methode für die Extraktion und Isolierung von PesticidrückstÄnden und UmweltchemikalienI. Das Prinzip der on-line Methode

     

Surface plasmon resonances of silver triangle nanoplates: graphic assignments of resonance modes and linear fittings of resonance peaks

The extinction spectra of five silver equilateral triangle plates with a fixed thickness of 10 nm and side lengths of 50, 100, 150, 200 ,and 250 nm, respectively, have been simulated by the discrete dipole approximation (DDA) method in which a geometric object of interest is meshed and represented by a lattice of spatial dipoles. Irradiated by an incident plane wave with a given propagation direction and polarization state, each triangle nanoplate presents three surface plasmon resonance (SPR) peaks in the range of 300 to 1200 nm. At a given peak, every complex spatial oscillatory vector derived by DDA (corresponding to a certain dipole in the meshed target) is orthogonally resolved into three basic oscillations. Each basic component can be subsequently expressed by two parameters, amplitude (P) and phase angle (varphi). The distributions of six such physical parameters of all the dipoles in the selected cross plane of the target are illustrated colorfully in plots as a graphic characterization and assignment of the SPR modes. The graphic method is applied to reveal the local fine features of SPR modes. And it provides direct evidence for classifying SPR peaks which belong to different triangle nanoplates and appear at different wavelengths. Three SPR modes are recognized graphically and the wavelengths of SPR peaks are found to have linear relationships with the side lengths of the triangle nanoplates.     

High-resolution analysis of (Sc3C2)@ C80 metallofullerene by third generation synchrotron radiation X-ray powder diffraction

The X-ray structure of Sc(3)C(82) is redetermined by the MEM/Rietveld method by using synchrotron radiation powder data at SPring-8, where the C(2) encapsulated structure available to discuss the Sc-Sc interatomic distances has been determined. The encapsulated three scandium atoms form a triangle shape. A spherical charge distribution originating from the C(2) molecule is located at the center of the triangle. Interatomic distances between Sc and Sc are 3.61(3) A in the triangle. The distance between Sc and the center of the C(2) molecule is 2.07(1) A.     

The Effect of an Input Signal with the Shape of an Arbitrary Triangle on Elution Curve Characteristics

The effect of an arbitrarily triangle input signal on the characteristics of elution curves has been studied. The numerical simulation of triangle input signals has shown that the additivity principle is fulfilled for the center of gravity and the second central moment (or variance) of an elution curve at an arbitrary adsorbent-layer length.