A novel high-spin heterometallic Ni12K4 cluster incorporating large Ni–azide circles and an in situ cyanomethylated di-2-pyridyl ketone

Reaction of di-2-pyridyl ketone (dpk) with nickel acetate and azide in the presence of potassium tert-butylate as a catalytic base generates the title compound, which contains the largest [Ni(m1,1-N3)]6 circles in the discrete ferromagnetically-coupled MII–azide cluster family, and shows an unprecedented in situ cyanomethylation of ketone.Clemente Juan, Juan Modesto, [email protected]

Magnetic exchange interaction in a pair of orbitally degenerate ions: Magnetic anisotropy of [Ti2Cl9]−3

The theory of the kinetic exchange in a pair of orbitally degenerate ions developed by the authors [J. Phys. Chem. A 102, 200 (1998)] is applied to the case of face-shared bioctahedral dimer (overall D3h-symmetry). The effective kinetic exchange Hamiltonian is found for a 2T2–2T2 system taking into account all relevant transfer pathways and charge-transfer crystal field states. The influence of different transfer integrals involved in the kinetic exchange on the energy pattern and magnetic properties of the system is examined. The role of other related interactions (trigonal crystal field, spin–orbit coupling) is also discussed in detail. Using the pseudoangular momentum representation and the technique of the irreducible tensor operators of R3-group we give a general outlook on the nontrivial symmetry properties of the effective Hamiltonian for the D3h-pair, and on the magnetic anisotropy arising from the orbital interactions specific for the case of orbital degeneracy. The magnetic properties of the binuclear unit [Ti2Cl9]−3 in Cs3Ti2Cl9 are discussed with a special emphasis on the magnetic anisotropy experimentally observed in this system. The existing exchange models for [Ti2Cl9]−3 and the concept of the effective Hamiltonian are discussed in the context of the present [email protected] ; [email protected] ; [email protected] ; [email protected]

High‐nuclearity mixed‐valence magnetic clusters : A general solution of the double exchange problem

We report here a general solution of the double‐exchange problem in the high‐nuclearity mixed valence systems containing arbitrary number P of the electrons delocalized over the network of N (P<N) localized spins. The developed approach is based on the successive (chainlike) spin‐coupling scheme and takes full advantage from the quantum angular momentum theory. In the framework of this approach the closed‐form analytical expressions are deduced for the matrix elements of the double exchange interaction, two‐electron transfer, and three‐center interaction that can be referred to as the potential exchange transfer. For the arbitrary nuclearity mixed‐valence systems the matrix elements of all named interactions are expressed in terms of all relevant spin quantum numbers and 6j symbols and do not contain higher order recoupling coefficients. We describe also the combined approach taking into account both angular momentum consideration and advantages of point symmetry adapted basis [email protected] , [email protected] ; [email protected] ; [email protected] ; [email protected]

A multi-redox responsive cyanometalate-based metallogel

A tetrathiafulvalene (TTF) based tridentate ligand (-(4’-methyl-4,5-di-n-dodecylthylthiotetrathiafulvalene-5’-ylthio)-’-[tris-2,2,2-(1-pyrazolyl)ethoxy]-p-xylene) (L) with long-chain alkyl moieties was prepared in order to obtain a new multi-redox active gelator based on a mixed-metal octanuclear complex [FeIII4NiII4(CN)12(tp)4(L)4](BF4)4 (1). The magnetism, electrochemistry and gelation behaviour of 1 were studied and 1,2-dichlorobenzene solutions of 1 are shown to display thermoreversible gelation behaviour at room temperature. Furthermore, the gel phase of 1 is shown to undergo room-temperature gel-to-sol transformations induced by both the oxidation and reduction of the gelator complex by F4TCNQ or [FeII(Cp*)2], respectively

Q-dependence of the inelastic neutron scattering cross section for molecular spin clusters with high molecular symmetry

For powder samples of polynuclear metal complexes the dependence of the inelastic neutron scattering intensity on the momentum transfer Q is known to be described by a combination of so called interference terms. They reflect the interplay between the geometrical structure of the compound and the spatial properties of the wave functions involved in the transition. In this work, it is shown that the Q-dependence is strongly interrelated with the molecular symmetry of molecular nanomagnets, and, if the molecular symmetry is high enough, is actually completely determined by it. A general formalism connecting spatial symmetry and interference terms is developed. The arguments are detailed for cyclic spin clusters, as experimentally realized by e.g. the octanuclear molecular wheel Cr8, and the star like tetranuclear cluster Fe4.Comment: 8 pages, 1 figures, REVTEX

Calculating the energy spectra of magnetic molecules: application of real- and spin-space symmetries

The determination of the energy spectra of small spin systems as for instance given by magnetic molecules is a demanding numerical problem. In this work we review numerical approaches to diagonalize the Heisenberg Hamiltonian that employ symmetries; in particular we focus on the spin-rotational symmetry SU(2) in combination with point-group symmetries. With these methods one is able to block-diagonalize the Hamiltonian and thus to treat spin systems of unprecedented size. In addition it provides a spectroscopic labeling by irreducible representations that is helpful when interpreting transitions induced by Electron Paramagnetic Resonance (EPR), Nuclear Magnetic Resonance (NMR) or Inelastic Neutron Scattering (INS). It is our aim to provide the reader with detailed knowledge on how to set up such a diagonalization scheme.Comment: 29 pages, many figure

Experimental Verification of the Gapless Point in the SS=1 Antiferromagnetic Bond Alternating Chain

Susceptibility and high field magnetization measurements have been performed on powder samples of an $S$=1 bond alternating chain compound [\{Ni(333-tet)($\mu$-N$_3$)\}$_n$](ClO$_4$)$_n$ (333-tet=tetraamine N,N'-bis(3-aminopropyl)-1,3-propanediamine). As the temperature is decreased, the susceptibility exhibits a round maximum at around 120 K and decreases gradually down to 10 K, and then falls down rapidly with a logarithmic curvature which is behavior of the susceptibility of a gapless or a nearly gapless antiferromagnetic chain. Magnetization up to 50 T at 1.4 K shows no or a very small gap in this compound. We have carried out numerical calculations for the $S$=1 antiferromagnetic bond alternating chain with various alternating ratios $\alpha$ and obtained a very good agreement between experiments and calculations for $\alpha$=0.6. We verify experimentally that the gapless point exists around $\alpha$=0.6.Comment: 12 pages, 4 Postscript figures, uses REVTE

Coming full circle: constructing a [Gd6] wheel dimer by dimer and the importance of spin topology

© 2017 The Royal Society of Chemistry. The syntheses, structures, magnetic and thermodynamic properties of three related triethanolamine-based Gd III complexes are described. The smallest, a dimer ([Gd 2 ]), can be viewed as the subunit from which the two larger complexes, a linear tetramer ([Gd 2 ] 2 ) and a cyclic hexamer ([Gd 2 ] 3 ), are composed by further deprotonation of the triethanolamine ligand. In all cases, nearest neighbour magnetic ions are weakly correlated by antiferromagnetic isotropic exchange, whose strength does not change significantly from one complex to another; J ranging from -0.10 to -0.13 cm -1 . Therefore, rather than the strength of the coupling, it is the spin topology that is the dominant factor in determining the differences between the physical properties-specifically, the nuclearity and the transition from open (dimer and tetramer) to cyclic (hexamer) boundary conditions. Indeed the hexanuclear wheel reaches the continuum limit of classical Heisenberg spin chains. In terms of the magnetocaloric properties, the smaller the nuclearity, the larger the magnetic entropy and adiabatic temperature changes