A Ferromagnetically Coupled (S=1) Peroxodicopper(II) Complex

Copper enzymes play important roles in the binding and activation of dioxygen in biological systems. Key copper/dioxygen intermediates have been identified and studied in synthetic analogues of the metalloprotein active sites, including the μ‐η²:η²‐peroxodicopper(II) motif relevant to type III dicopper proteins. Herein, we report the synthesis and characterization of a bioinspired dicopper system that forms a stable μ‐η¹:η¹‐peroxo complex whose Cu‐O‐O‐Cu torsion is constrained to around 90° by ligand design. This results in sizeable ferromagnetic coupling between the copper(II) ions, which is detected by magnetic measurements and HF‐EPR spectroscopy. The new dicopper peroxo system is the first with a triplet ground state, and it represents a snapshot of the initial stages of O₂ binding at type III dicopper sites.     

A rare ligand bridged ferromagnetically coupled MnIV3 complex with a ground spin state of S = 9/2

An exclusively chelating ligand bridged high-valent [MnIV3] complex has been synthesized, in which all Mn(IV) ions are ferromagnetically-coupled to exhibit an S(T) = 9/2 spin ground state.     

The NaK 1(b) 3Pi(Omega=0) state hyperfine structure and the 1(b) 3Pi(Omega=0) approximately 2(A) 1Sigma+ spin-orbit interaction

We have measured the hyperfine structure of mutually perturbing rovibrational levels of the 1(b) 3Pi0 and 2(A) 1Sigma+ states of the NaK molecule, using the perturbation-facilitated optical-optical double resonance method with copropagating lasers. The unperturbed 1(b) 3Pi0 levels are split into four hyperfine components by the Fermi contact interaction bFIS. Mixing between the 1(b) 3Pi0 and 2(A) 1Sigma+ levels imparts hyperfine structure to the nominally singlet component of the perturbed levels and reduces the hyperfine splitting of the nominally triplet component. Theoretical analysis relates these observations to the hyperfine splitting that each 1(b) 3Pi0 level would have if it were not perturbed by a 2(A) 1Sigma+ level. Using this analysis, we demonstrate that significant hyperfine splitting arises because the 1(b) 3Pi0 state cannot be described as pure Hund's case (a). We determine bF for the 1(b) 3Pi0 levels and also a more accurate value for the magnitude of the singlet-triplet spin-orbit coupling HSO=[1(b) 3Pi0(vb,J)(H(SO))2(A) 1Sigma+(vA,J). Using the known spectroscopic constants of the 1(b) 3Pi state, we obtain bF=0.009 89+/-0.000 27 cm(-1). The values of (H(SO)) are found to be between 2 and 3 cm(-1), depending on vb, vA, and J. Dividing (H(SO)) by calculated vibrational overlap integrals, and taking account of the 1(b) 3Pi(Omega) rotational mixing, we can determine the magnitude of the electronic part H(el) of H(SO). Our results yield (H(el))=(16.33+/-0.15) cm(-1), consistent with our previous determinations using different techniques.     

Conformationally constrained, stable, triplet ground state (S = 1) nitroxide diradicals. Antiferromagnetic chains of S = 1 diradicals

Nitroxide diradicals, in which nitroxides are annelated to m-phenylene forming tricyclic benzobisoxazine-like structures, have been synthesized and characterized by X-ray crystallography, magnetic resonance (EPR and 1H NMR) spectroscopy, as well as magnetic studies in solution and in solid state. For the octamethyl derivative of benzobisoxazine nitroxide diradical, the conformationally constrained nitroxide moieties are coplanar with the m-phenylene, leading to large values of 2J (2J/k > 200 K in solution and 2J/k > 300 K in the solid state). For the diradical, in which all ortho and para positions of the m-phenylene are sterically shielded, distortion of the nitroxide moieties from coplanarity is moderate, such that the singlet-triplet gaps remain large in both solution (2J/k > 200 K) and the solid state (2J/k approximately 400-800 K), though an onset of thermal depopulation of the triplet ground state is detectable near room temperature. These diradicals have robust triplet ground states with strong ferromagnetic coupling and good stability at ambient conditions. Magnetic behavior of the nitroxide diradicals at low temperature is best fit to the model of one-dimensional S = 1 Heisenberg chains with intrachain antiferromagnetic coupling. The antiferromagnetic coupling between the S = 1 diradicals may be associated with the methyl nitroxide C-H- - -O contacts, including nonclassical hydrogen bonds. These unprecedented organic S = 1 antiferromagnetic chains are highly isotropic, compared to those of the extensively studied Ni(II)-based chains.     

Spin maximization: switching of the usual S = 11 state of Mn(II)4Mn(III)3 disklike complexes to the maximum S = 16

The S = 11 ground states of the Mn 7 family of mixed-valence complexes with a metal-centered hexagonal topology have been found by density functional theory calculations to arise by spin frustration involving small differences in the magnitudes of the two weakest interactions controlling the alignment of the central spin. Targeted structural perturbation has allowed a complex with the central spin flipped to be discovered, which thus possesses the maximum S = 16 ground state.     

Slow magnetic relaxation of a ferromagnetic Ni(II)5 cluster with an S = 5 ground state

Complex [Ni 5{pyCOpyC(O)(OMe)py} 2(O 2CMe) 4(N 3) 4(MeOH) 2].2MeOH.2.6H 2O ( 1.2MeOH.2.6H 2O) was synthesized by the reaction of Ni(O 2CMe) 2.4H 2O with pyCOpyCOpy and NaN 3 in refluxing MeOH. It crystallizes in the monoclinic C2/ c space group and consists of five Ni (II) atoms in a helical arrangement. Direct current magnetic susceptibility studies reveal ferromagnetic interactions between the Ni (II) ( S = 1) ions, stabilizing an S = 5 ground state. Alternating current susceptibility experiments revealed the existence of out-of-phase signals indicative of slow magnetic relaxation. Analysis of the signals showed that they are composite, suggesting more than one relaxation process, while analysis of their magnitudes suggests not all molecules undergo slow magnetic relaxation. Magnetization field-sweep experiments revealed hysteresis at 1.8 K, and magnetization decay experiments clearly verified the appearance of slow magnetic relaxation at that temperature.     

Spin-frustrated trinuclear Cu(II) clusters with mixing of 2(S = 1/2) and S = 3/2 states by antisymmetric exchange. 1. Dzialoshinsky-Moriya exchange contribution to zero-field splitting of the S = 3/2 state

The mixing of the spin-frustrated 2(S = 1/2) and S = 3/2 states by the Dzialoshinsky-Moriya (DM) exchange is considered for the Cu 3(II) clusters with strong DM exchange coupling. In the antiferromagnetic Cu 3 clusters with strong DM interaction, the 2(S = 1/2)-S = 3/2 mixing by the in-plane DM exchange ( G x ) results in the large positive contribution 2 D DM > 0 to the axial zero-field splitting (ZFS) 2 D of the S = 3/2 state. The correlations between the ZFS 2 D DM of the excited S = 3/2 state, sign of G z and chirality of the ground-state were obtained. In the isosceles Cu 3 clusters, the in-plane DM exchange mixing results in the rhombic magnetic anisotropy of the S = 3/2 state. Large distortions result in an inequality of the pair DM parameters, that leads to an additional magnetic anisotropy of the S = 3/2 state. In the {Cu 3} nanomagnet, the in-plane DM exchange (Gx, Gy) mixing results in the 58% contribution 2 D DM to the observed ZFS 2 D of the S = 3/2 state. The DM exchange and distortions explain the experimental observation that the intensities of the electron paramagnetic resonance (EPR) transitions arising from the 2(S = 1/2) group of levels of the {Cu 3} nanomagnet are comparable to each other and are 1 order of magnitude weaker than that of the S = 3/2 state. In the ferromagnetic Cu 3 clusters, the in-plane DM exchange mixing of the excited 2(S = 1/2) and the ground S = 3/2 states results in the large negative DM exchange contribution 2 D DM' < 0 to the axial ZFS 2 D of the ground S = 3/2 state.     

Six-fold oxygen-coordinated triplet (S = 1) palladium(II) moieties templated by tris(bipyridine)ruthenium(II) ions

Tris(bipyridine)ruthenium(II) is used as a templating agent to insert palladium(II) into three-dimensional oxalate-based networks. The templated-assembly of [Ru(bpy)(3)][Pd(2)(ox)(3)] (Pd(2)) and [Ru(bpy)(3)][PdMn(ox)(3)] (PdMn) is described. The latter compound is structurally characterized by powder X-ray diffraction and X-ray absorption spectroscopy. These techniques reveal an unusual 6-fold oxygen environment around the Pd(II) atoms with two short (2.02 Angstrom) and four long (2.17 Angstrom) Pd-O distances. As stated by magnetometry, this environment is associated with a triplet ground state (S = 1) of the palladium(II) ion: when the temperature is decreased, the chiMT product shows a monotonous decrease from 5.54 cm(3) K mol(-1) at 300 K, a value which is slightly lower than the one expected for independent paramagnetic Pd(II) (S = 1, g = 2) and Mn(II) (S = 5/2, g = 2) ions. This thermal variation is due to antiferromagnetic exchange interactions between the two spin bearers. Nevertheless, no long-range magnetic order is detected down to 2 K. These results are confirmed by an analysis of the [MII(C(2)O(4))(3)](4-) (M = Ni, Pd, Pt) complex and of a [Pd(II){mu-(C(2)O(4))Mn(II)(OH(2))(4)}(3)](2+) tetranuclear model using density functional theory.     

Measurement of the ground state hyperfine splitting in207Pb II

The ground state hyperfine splitting of simply ionized lead has been determined using pulsed laser excitation of electrodynamically confined ions. We obtain ΔV(6P_1/2)=12.85(10) GHz     

Density functional calculations of a tetradecametallic iron(III) cluster with a very large spin ground state

Density functional theory (DFT) calculations and Monte Carlo (MC) simulations are used to calculate the exchange interactions in the Fe(III) cluster [Fe14(bta)6O6(OMe)18Cl6], impossible to determine by conventional methods--the results support a huge ground state spin arising from competing antiferromagnetic interactions.     

Investigation of the hyperfine structure of TaI-line (II)

The hyperfine structure of several spectral lines of the neutral tantalum atom was investigated by means of saturated laser spectroscopy, detecting optogalvanic signals and/or laser induced fluorescence. From the spectra we could determine the magnetic hyperfine interaction constants A and the electric quadrupol interaction constants B of 11 levels of even parity and 13 levels of odd parity.     

On the hyperfine coupling in tetragonal copper(II) complexes

The vibronic effect on the hyperfine coupling (HFC) parameters in tetragonal copper(II) complexes was studied. The parameters of the vibronic contributions from the - and 4s-AOs of the Cu²⁺ ion to the ground-state function were estimated. The anomalous behavior of the isotropic HFC was analyzed in terms of the static model with consideration of the vibronic coupling. The static and vibronic contributions to the anisotropic portions of the components of the HFC tensor were estimated.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 204–206.Original Russian Text Copyright © 2005 by Muravev.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Ag(nic)2 (nic = nicotinate): a spin-canted quasi-2D antiferromagnet composed of square-planar S = 1/2 Ag(II) ions

Square-planar S = 1/2 Ag(II) ions in polymeric Ag(nic)(2) are linked by bridging nic monoanions to yield 2D corrugated sheets. Long-range magnetic order occurs below T(N) = 11.8(2) K due to interlayer couplings that are estimated to be about 30 times weaker than the intralayer exchange interaction.     

Peculiarity in the electronic structure of Cu(II) complex ferromagnetically coupled with bisimino nitroxides

By means of the electron spin resonance (ESR) technique, we have investigated the electronic structures of the tridentate imino nitroxyl diradical complex with copper(II) (Cu-bisimpy), which has a square planar structure and a ground quartet state with an extremely strong ferromagnetic exchange interaction, and its related compounds (bisimpy = 2,6-bis(1'-oxyl-4',4',5',5'-tetramethyl-4',5'-dihydro-1' H-imidazol-2'-yl)pyridine). It was clarified that Cu-bisimpy had unique magnetic orbitals, compared with the biradical ligand (bisimpy), a zinc(II) biradical complex (Zn-bisimpy) and a copper(II) terpyridine complex (Cu-tpy) (tpy = 2,2';6',2'-terpyridine). Multifrequency ESR spectroscopy provided a reliable set of magnetic parameters of Cu-bisimpy, which has a small g anisotropy ( g x = 2.02, g y = 2.01, g z = 2.08) and small hyperfine coupling with Cu (|A x| = 42.0 MHz, |A y|相似文献