Superexchange Paths Research Articles

Investigation of optical and magnetic properties of 3d-4d transition metal ion based double Perovskite: Sr2MnRuO6

Investigation of physical properties in double perovskites, A2B′B″O6, containing 3d/4d transition metal ions at the B sites is an interesting avenue of research. In this study, we focus on Sr2MnRuO6, exploring its structural, morphological, optical and magnetic properties. Sr2MnRuO6 was synthesized in single phase using solid-state reaction route. It crystallizes in a tetragonal structure (space group I4/mcm, #140) with lattice parameters a = 5.4633 (2) Å, c = 7.9419 (1) Å. X-ray diffraction analysis revealed no super lattice reflections, indicating disorder in the B-site cations.The Jahn-Teller distortion in Mn-O6 octahedra,as revealed by XRD results, indicates a high spin state for the Mn3+ ion. The stoichiometric ratio of Sr: Mn: Ru (∼2:1:1), as determined by bond valence sum calculations and confirmed by energy dispersive x-ray spectroscopy agree well with the nominal composition of Sr2MnRuO6. Diffuse reflectance spectroscopy showed strong absorption throughout the visible region with a direct band gap of ∼3 eV, indicating Sr2MnRuO6 is a potential candidate for optical applications. Huge photoluminescence emission observed in the visible region is attributed to Mn3+ ions. The temperature dependence of molar susceptibility data indicates a paramagnetic to antiferromagnetic transition around 195 K. The possible super exchange paths for antiferromagnetic interaction are Ru5+- 4d3 (t2g3eg0) − O1 − Ru5+- 4d3 (t2g3eg0) along the z axis, or Ru5+- 4d3 (t2g3eg0) − O2 − Ru5+- 4d3 (t2g3eg0) in the xy-plane, with the angles between these orbitals being nearly 180°. At low temperatures under a 10,000 Oe field, spin glass type magnetic behaviour is observed. The effective magnetic moment (6.17 μB) obtained from the Curie-Weiss fit from 260 K to 290 K nearly matched with the theoretical resultant effective moment (6.24 μB) by considering Mn3+ ions in HS state and Ru5+ ions.Specific heat measurements revealed no long-range magnetic ordering down to 2 K, further suggesting the role of cationic disorder in the magnetic behaviour of Sr2MnRuO6.

Crystal Structure of Bismuth-Containing Samarium Iron–Aluminium Borates Sm1−xBixFe3−yAly(BO3)4 (x = 0.05–0.07, y = 0–0.28) in the Temperature Range of 25–500 K

Structural features of new mixed bismuth-containing samarium iron–aluminium borate single crystals Sm1−xBixFe3−yAly(BO3)4 (x = 0.05–0.07, y = 0–0.28) were studied using X-ray diffraction analysis based on aluminium content and temperature in the range 25–500 K. The crystals were grown using the solution-in-melt technique with Bi2Mo3O12 in a flux. The composition of the single crystals was analyzed using energy-dispersive X-ray fluorescence and energy-dispersive X-ray elemental analysis. Temperature dependencies of Sm1−xBixFe3−yAly(BO3)4 unit-cell parameters were studied. Negative thermal expansion was identified below 100 K and represented by characteristic surfaces of the thermal expansion tensor. (Sm,Bi)–O, (Sm,Bi)–(Fe,Al), (Fe,Al)–(Fe,Al), and (Fe,Al)–O interatomic distances decreased with the addition of aluminium atoms. An increase in the (Fe,Al)–(Fe,Al) intrachain bond length at low temperatures in the magnetically ordered state weakened this bond, whereas a decrease in the (Fe,Al)–(Fe,Al) interchain distance strengthened super-exchange paths between different chains. It was found that the addition of aluminium atoms influenced interatomic distances in Sm1−xBixFe3−yAly(BO3)4 much more than lowering the temperature from 293 K to 25 K. The effect of aluminium doping on magnetoelectric properties and structural symmetry of rare-earth iron borates is also discussed.

Two-dimensional Heisenberg model with material-dependent superexchange interactions

The two-dimensional (2D) van der Waals ferromagnetic semiconductors, such as CrI$_3$ and Cr$_2$Ge$_2$Te$_6$, and the 2D ferromagnetic metals, such as Fe$_3$GeTe$_2$ and MnSe$_2$, have been obtained in recent experiments and attracted a lot of attentions. The superexchange interaction has been suggested to dominate the magnetic interactions in these 2D magnetic systems. In the usual theoretical studies, the expression of the 2D Heisenberg models were fixed by hand due to experiences. Here, we propose a method to determine the expression of the 2D Heisenberg models by counting the possible superexchange paths with the density functional theory (DFT) and Wannier function calculations. With this method, we obtain a 2D Heisenberg model with six different nearest-neighbor exchange coupling constants for the 2D ferromagnetic metal Cr$_3$Te$_6$, which is very different for the crystal structure of Cr atoms in Cr$_3$Te$_6$. The calculated Curie temperature Tc = 328 K is close to the Tc = 344 K of 2D Cr$_3$Te$_6$ reported in recent experiment. In addition, we predict two stable 2D ferromagnetic semiconductors Cr$_3$O$_6$ and Mn$_3$O$_6$ sharing the same crystal structure of Cr$_3$Te$_6$. The similar Heisenberg models are obtained for 2D Cr$_3$O$_6$ and Mn$_3$O$_6$, where the calculated Tc is 218 K and 208 K, respectively. Our method offers a general approach to determine the expression of Heisenberg models for these 2D magnetic semiconductors and metals, and builds up a solid basis for further studies.

Synthesis and Characterization of Oxide Chloride Sr2VO3Cl, a Layered S = 1 Compound.

The mixed-anion compound with composition Sr2VO3Cl has been synthesized for the first time, using the conventional high-temperature solid-state synthesis technique in a closed silica ampule under inert conditions. This compound belongs to the known Sr2 TmO3Cl (Tm = Sc, Mn, Fe, Co, Ni) family, but with Tm = V. All homologues within this family can be described with the tetragonal space group P4/nmm (No. 129); from a Rietveld refinement of powder X-ray diffraction data on the Tm = V homologue, the unit cell parameters were determined to a = 3.95974(8) and c = 14.0660(4) Å, and the atomic parameters in the crystal structure could be estimated. The synthesized powder is black, implying that the compound is a semiconductor. The magnetic investigations suggest that Sr2VO3Cl is a paramagnet at high temperatures, exhibiting a μeff = 2.0 μB V-1 and antiferromagnetic (AFM) interactions between the magnetic vanadium spins (θCW = -50 K), in line with the V-O-V advantageous super-exchange paths in the V-O layers. Specific heat capacity studies indicate two small anomalies around 5 and 35 K, which however are not associated with long-range magnetic ordering. 35Cl ss-NMR investigations suggest a slow spin freezing below 4.2 K resulting in a glassy-like spin ground state.

Mechanism of carrier doping induced magnetic phase transitions in two-dimensional materials

Electrically tuning long-range magnetic orders has been realized in two-dimensional (2D) semiconductors via electrostatic doping. On the other hand, the observations are highly diverse: the transition can be realized by either electrons or holes or both depending on specific materials. Moreover, doped carriers seem to always favor the ferromagnetic (FM) ground state. The mechanism behind those diverse observations remains uncovered. Combining first-principles simulations, we analyze the spin superexchange paths of the correlated d/f orbitals around band edges and assign 2D magnetic semiconductors into three types by their projected density of states (PDOS). We find that each type of PDOS corresponds to a specific carrier-driven magnetic phase transition and the critical doping density and type of carriers can be quantitatively obtained by calculating the superexchange coupling strength. The model results are in good agreements with first-principles calculations and available measurements. After understanding the mechanism, we can design heterostructures to realize the FM to antiferromagnetic transition, which has not been realized before. This model is helpful to understand diverse measurements and expand the degrees of freedom to control long-range magnetic orders in 2D semiconductors.

Crystal Structure Dynamics of RFe3(BO3)4 Single Crystals in the Temperature Range 25–500 K

The multiferroic RFe3(BO3)4 family is characterized by diverse magnetic, magnetoelectric, and magnetoelastic properties, the fundamental aspects of which are essential for modern electronics. The present research, using single-crystal X-ray diffraction (XRD) and Mössbauer spectroscopy (MS) in the temperature range of 25–500 K, aimed to analyze the influence of local atomic coordination on magnetoelectric properties and exchange and super-exchange interactions in RFe3(BO3)4. Low-temperature, single-crystal XRD data of the magnetically ordered phase of RFe3(BO3)4 at 25 K, which were obtained for the first time, were supplemented with data obtained at higher temperatures, making it possible to draw conclusions about the mechanism of the structural dynamics. It was shown that, in structures with R = Gd, Ho, and Y (low-temperature space group P3121), a shift in oxygen atoms (O2, second coordination sphere of R atoms) was accompanied by rotation of the B2O3 triangle toward R atoms at low temperatures, and by different rearrangements in iron chains of two types, in contrast to Nd and Sm iron borates (space group R32). These rearrangements in the structures of space group P3121 affected the exchange and super-exchange paths at low temperatures. The MS results confirm the influence of the distant environment of atoms on the magnetoelectric properties of rare-earth iron borates at low temperatures.

Hole-mediated ferromagnetic coupling in two-dimensional CrI3/VSe2 van der Waals heterostructures

Two-dimensional (2D) ferromagnetic (FM) semiconductors play imperative roles in the development of spintronic devices. However, the Curie temperature (Tc) of most 2D FM semiconductors are fairly low for practical applications. Herein, using the first-principles calculations, it revealed that the magnetic coupling strength within CrI3 can be modulated via the construction of CrI3/VSe2 van der Waals heterostructure. The system remains semiconducting with the band gap of 0.22 eV (GGA level). Its Tc can be boosted to ∼210 K via p-type doping, well above the liquid nitrogen temperature, which makes it a step closer to practical application. The greatly promoted FM coupling is originated from the additional super-exchange paths as well as the enhanced in-plane Cr-I-Cr super-exchange interaction. It is found that the interlayer magnetic coupling is tunable upon the stacking alignment, which is feasible to manipulate the magnetic orders using external mechanical motion.

Tunable magnetic coupling and high Curie temperature of two–dimensional PtBr3via van der waals heterostructures

Two-dimensional ferromagnetic semiconductors hold great promise for next-generation spintronic applications. However, candidates with high Curie temperature (Tc) are still lacking. Using the first-principles calculations, the PtBr3 monolayer is found to exhibit ferromagnetic order above the room temperature. The formation of PtBr3/WSe2 van der Waals heterostructures can increase the Tc to ∼ 410 K by additional super-exchange path of Pt-Se-Pt. The spin-exchange interactions for this path is as strong as ∼ 22 meV, which is superior to most other magnetic system. The out-of-plane compression further boosts the Tc to ∼ 636 K. The interlayer magnetic coupling is highly tunable depending on the stacking alignment, which closes or weakens some super-exchange channels. In addition, the interlayer interaction leads to a phase transition from half-metal to semiconductor, which greatly promotes its potential in spintronic applications. The strong stacking dependent feature is feasible to manipulate the magnetic orders by external strain or mechanical motion.

High thermal stability of anti-ferromagnetic coupled molecules with FeCo layers

We propose the optimization of the magnetic remanence and the thermal stability of Mn phthalocyanine coupled with a ferromagnetic substrate, by exploiting interlayer exchange coupling within an advanced organic spin interface architecture, constituted by a FeCo film covered by a graphene membrane, hosting the MnPc molecular layer. The challenge to obtain magnetic remanence for molecular systems stable up to room temperature has been accomplished thanks to a super-exchange path, mediated by the π orbital of the organic ligands of the molecule and of the graphene sheet, favoring an antiferromagnetic (AFM) alignment for the MnPc molecules with the FeCo film. This spin interface with a strong AFM coupling mediated by a graphene spacer is optimized against thermal fluctuations, presenting a well defined remanence even at room temperature, as demonstrated by the persistent dichroic signal in temperature-dependent circularly polarized x-ray absorption spectra.

Antiferromagnetic Order and Spin-Canting Transition in the Corrugated Square Net Compound Cu3(TeO4)(SO4)·H2O.

Strongly correlated electrons in layered perovskite structures have been the birthplace of high-temperature superconductivity, spin liquids, and quantum criticality. Specifically, the cuprate materials with layered structures made of corner-sharing square-planar CuO4 units have been intensely studied due to their Mott insulating ground state, which leads to high-temperature superconductivity upon doping. Identifying new compounds with similar lattice and electronic structures has become a challenge in solid-state chemistry. Here, we report the hydrothermal crystal growth of a new copper tellurite sulfate, Cu3(TeO4)(SO4)·H2O, a promising alternative to layered perovskites. The orthorhombic phase (space group Pnma) is made of corrugated layers of corner-sharing CuO4 square-planar units that are edge-shared with TeO4 units. The layers are linked by slabs of corner-sharing CuO4 and SO4. Using both the bond valence sum analysis and magnetization data, we find purely Cu2+ ions within the layers but a mixed valence of Cu2+/Cu+ between the layers. Cu3(TeO4)(SO4)·H2O undergoes an antiferromagnetic transition at TN = 67 K marked by a peak in the magnetic susceptibility. Upon further cooling, a spin-canting transition occurs at T* = 12 K, evidenced by a kink in the heat capacity. The spin-canting transition is explained on the basis of a J1-J2 model of magnetic interactions, which is consistent with the slightly different in-plane superexchange paths. We present Cu3(TeO4)(SO4)·H2O as a promising platform for the future doping and strain experiments that could tune the Mott insulating ground state into superconducting or spin liquid states.

Infrared phonon spectroscopy on the Cairo pentagonal antiferromagnet Bi2Fe4O9 : A study through the pressure-induced structural transition

Magnetic and crystallographic transitions in the Cairo pentagonal magnet ${\mathrm{Bi}}_{2}{\mathrm{Fe}}_{4}{\mathrm{O}}_{9}$ are investigated by means of infrared synchrotron-based spectroscopy as a function of temperature (20--300 K) and pressure (0--15.5 GPa). One of the phonon modes is shown to exhibit an anomalous softening as a function of temperature in the antiferromagnetic phase below 240 K, highlighting spin-lattice coupling. Moreover, under applied pressure at 40 K, an even larger softening is observed through the pressure-induced structural transition. Lattice dynamical calculations reveal that this mode is indeed very peculiar as it involves a minimal bending of the strongest superexchange path in the pentagonal planes, as well as a decrease in the distances between second-neighbor irons. The latter confirms the hypothesis made by Friedrich et al., [J. Phys.: Condens. Matter 24, 145401 (2012)] about an increase in the oxygen coordination of irons being at the origin of the pressure-induced structural transition. As a consequence, one expects a new magnetic superexchange path that may alter the magnetic structure under pressure.

Oxygen vacancy-induced short-range ordering as a sole mechanism for enhanced magnetism of spinel ZnFe2O4 prepared via a one-step treatment

Despite being difficult to identify, extremely dilute oxygen vacancies have been widely reported to play an important role in enhancing magnetism in ZnFe2O4. The mechanisms underlying this enhanced magnetism have not been well understood for a long time and remain controversial because the formation of oxygen vacancy-rich ZnFe2O4 can be accompanied by changes in the chemical/physical characteristics, especially the composition, particle size, surface morphology and cation distribution, which can significantly affect the magnetization. An open and important question is whether and to what extent the enhanced magnetization can be attributed only to oxygen vacancies. In this study, the relationship between the magnetization and oxygen vacancies in ZnFe2O4 was definitively determined by using a carefully designed “shake-and-heat” treatment to prepare vacancy-rich samples while keeping the other crystal/surface parameters constant. Compared to the nearly vacancy-free paramagnetism samples, the vacancy-rich samples exhibited a higher magnetization of approximately 5 emu/g at both 300 K and 2 K. The Fe3+-O2--Fe3+ superexchange paths broken by oxygen vacancies then resulting in the Fe3+-Fe3+ ferromagnetism configuration. Meanwhile, the oxygen vacancy is highly diluted then the ferromagnetism configuration is confined in a single super-cell, favoring a short-range magnetic ordering at room temperature. The concentration of oxygen vacancies was calculated to be 0.68% by magnetization measurement. Our results may shed a light on how oxygen vacancies affect magnetism.

Microscopic Mechanism for a Higher-Spin Kitaev Model.

The spin S=1/2 Kitaev honeycomb model has attracted significant attention since emerging candidate materials have provided a playground to test non-Abelian anyons. The Kitaev model with higher spins has also been theoretically studied, as it may offer another path to a quantum spin liquid. However, a microscopic route to achieve higher spin Kitaev models in solid state materials has not been rigorously derived. Here we present a theory of the spin S=1 Kitaev interaction in two-dimensional edge-shared octahedral systems. Essential ingredients are strong spin-orbit coupling in anions and strong Hund's coupling in transition metal cations. The S=1 Kitaev and ferromagnetic Heisenberg interactions are generated from superexchange paths. Taking into account the antiferromagnetic Heisenberg term from direct-exchange paths, the Kitaev interaction dominates the physics of the S=1 system. Using an exact diagonalization technique, we show a finite regime of S=1 spin liquid in the presence of the Heisenberg interaction. Candidate materials are proposed, and generalization to higher spins is discussed.

Weak ferromagnetism and time-stable remanence in hematite: effect of shape, size and morphology

A number of Dzyaloshinskii–Moriya interaction (DMI) driven canted antiferromagnets or weak ferromagnets (WFM) including hematite exhibit two distinct time scales in magnetization relaxation measurements, one of which is ultra-slow. This leads to the observation of a part of remanence that is time-stable in character. In this work, our endeavor is to optimize the magnitude of this time-stable remanence for the hematite, a room temperature WFM, as a function of shape size and morphology. A substantial enhancement in the magnitude of this unique remanence is observed in porous hematite, consisting of ultra-small nano particles, as compared to crystallites grown in regular morphology, such as cuboids or hexagonal plates. This time-stable remanence exhibits a peak-like pattern with magnetic field, which is significantly sharper in porous sample. Experimental data suggest that the extent and the magnitude of the spin canting associated with the WFM phase can be best gauged by the presence of this remanence and its unusual magnetic field dependence. Temperature variation of lattice parameters bring out correlations between strain effects that alter the bond length and bond angle associated with primary super exchange paths, which in-turn systematically alter the magnitude of the time-stable remanence. This study provides insights regarding a long standing problems of anomalies in the magnitude of magnetization on repeated cooling in case of hematite. Our data caps on these anomalies, which we argue, arise due to spontaneous spin canting associated with WFM phase. Our results also elucidate on why thermal cycling protocols during bulk magnetization measurements are even more crucial for hematite which exhibits both canted as well as pure antiferromgnetic phase.

Exciton-Phonon Interaction Model for Singlet Fission in Prototypical Molecular Crystals.

In singlet fission (SF), a spin-conserving splitting of one singlet exciton into two triplet excitation states, the transition between localized electronic states can be controlled and modulated by delocalized lattice phonons. In this work, we built an exciton-phonon (ex-ph) interaction model accounting local electronic states coupled with both local molecular vibrations and low frequency intermolecular phonon modes for SF in crystalline tetracene and rubrene. On the basis of the calculated electronic couplings at the equilibrium structure of the molecular dimer, a superexchange path for SF was found for tetracene while couplings between the triplet pair (TT) state and other diabatic states are zero for rubrene due to the high symmetry. Our further ex-ph spectral density analysis and quantum dynamics simulation based on our ex-ph interaction model suggested a thermal-activated mechanism for SF in rubrene crystal via symmetry breaking by nuclear vibration, which is in agreement with recent experiments. It is also shown that thermal fluctuations of electronic couplings in both tetracene and rubrene are mostly in the same order of magnitude at room temperature, and this could be one of the reasons for both tetracene and rubrene to exhibit SF time scales within a close range (hundreds to thousands of femtoseconds) in experiments.

Synthesis, structure and magnetic properties of Ti doped La2MnNiO6 double perovskite

We report sol-gel synthesis, structural characterization and magnetic properties of La2Mn1-xTixNiO6 (0 ≤ x ≤ 1.0). Ti doping removed the biphasic structure of La2MnNiO6 by suppression of rhombohedral structure and all the Ti containing samples crystallized in monoclinic P21/n symmetry. La2MnNiO6 exhibits multiple magnetic transitions. The high temperature ferromagnetic transition of La2MnNiO6 gradually shifted to lower temperatures with increase in Ti doping. La2TiNiO6 (x = 1.0) does not show any long-range magnetic ordering. The suppression of magnetic transition by Ti doping is ascribed to the destruction of Mn4+—O—Ni2+ superexchange interaction. However, the signature of ferromagnetic phase persists up to 70% Ti doping, indicating the robustness of magnetic ordering in La2MnNiO6. These results suggest that the addition of Ti4+ truncates the ferromagnetic Mn4+—O—Ni2+ superexchange path and it likely promotes ferromagnetic cluster formation. The robustness of ferromagnetic state towards Ti substitution compared to the simple perovskite or spinel structure can be attributed to cationic ordering in double perovskite structure. Both the pure and Ti-doped samples exhibit magnetic frustration at lower temperatures due to partial cationic disordering. The absence of long-range ordering in La2TiNiO6, unlike La2TiCoO6 or Pr2TiCoO6, could be related to cationic disordering.

Hamiltonian of the S=12 dimerized antiferromagnetic-ferromagnetic quantum spin chain BaCu2V2O8

The novel quantum magnet ${\mathrm{BaCu}}_{2}{\mathrm{V}}_{2}{\mathrm{O}}_{8}$ was recently discovered to be a rare physical realization of a one-dimensional antiferromagnetic-ferromagnetic dimerized chain which displays strongly correlated phenomena at elevated temperatures [E. S. Klyushina et al., Phys. Rev. B 93, 241109(R) (2016)]. This paper presents an extended study of the Hamiltonian of ${\mathrm{BaCu}}_{2}{\mathrm{V}}_{2}{\mathrm{O}}_{8}$ at base temperature. Static susceptibility and inelastic neutron scattering data are compared to several theoretical models. An analytical relation for the dynamic structure factor of the complex unit cell of ${\mathrm{BaCu}}_{2}{\mathrm{V}}_{2}{\mathrm{O}}_{8}$ is derived and used to identify the intrachain exchange paths. Further analysis using the first moment of the dynamic structure factor was employed to determine the exchange path responsible for the intradimer interaction. This analysis reveals that the dimer chain is formed by a dominant antiferromagnetic exchange interaction ${J}_{\mathrm{intra}}=40.92\phantom{\rule{0.28em}{0ex}}\mathrm{meV}$ which is realized via the Cu-O-V(II)-O-Cu superexchange path and a weak ferromagnetic coupling ${J}_{\mathrm{inter}}=\ensuremath{-}11.97$ meV which arises within the copper-oxygen double plaquettes.

Discovery of a new type of magnetic order on pyrochlore spinels

Frustration in spin system can give rise to unique ordered states and as a consequence several physical phenomena are expected such as multiferroics, high temperature superconductors and anomalous hall effect. Here we report the "new magnetic orders" induced by anisotropic spin exchanges on pyrochlore spinels as the interplay of spin orbit coupling and geometrical frustration. Due to complicated superexchange paths of B-site spinels, we claim that anisotropic interaction between next-nearest neighbors play an important role. Based on the systematic studies of generic spin model, we argue that several classical spin states can be explored in spinel systems; local XY state, all-in all-out state, Palmer-Chalker state and coplanar spiral state. In addition, we reveal new types of magnetic phases with finite ordering wavevectors, labeled as 'octagonal (prism)' state and '(distorted) cubic' states. When the 'octagonal prism' state is stabilized, non-zero scalar spin chirality induces alternating net current in addition to finite orbital current and orbital magnetization even in Mott insulators. Finally, we also discuss the relevance of 'distorted cubic' state to the magnetic order of spinel compound GeCo2O4.

Comparative Study of Electronic Structure and Magnetic Properties of Osmate Double Perovskites: Ca2FeOsO6versus Ca2Co(Ni)OsO6

Employing density functional theory, we study the trend in the electronic and magnetic properties of 3d–5d double perovskites, upon varying the 3d element for a fixed choice of 5d element, namely Ca2BOsO6 (B = Fe/Co/Ni). While all three compounds are reported to be ferrimagnets, the magnetic transition temperature of Ca2FeOsO6 is reported to be 2–2.4 times larger than that of Ca2CoOsO6 or Ca2NiOsO6. Our first-principles study provides microscopic insight into this trend. This trend is found to be caused by the downward shift in the position of d level energies of the B site element with respect to that of the Os t2g level upon moving across the 3d series from Fe to Co and Ni. This in turn changes the nominal valence of the Os ion from 5+ in Ca2FeOsO6 to 6+ in Ca2CoOsO6 and Ca2NiOsO6, resulting in differing superexchange paths between Ca2FeOsO6 and Ca2Co(Ni)OsO6, and additionally enabling the hybridization-mechanism-driven magnetism in Ca2FeOsO6. These together significantly enhance the magnetic transition...

Experimental and theoretical investigations on magneto-structural correlation in trinuclear copper(II) hydroxido propellers

The trinuclear copper(II) compounds [Cu3(μ3-OH)(GL1)3](ClO4)2 (1–4) and [Cu3(μ3-OH)(GL2)3](ClO4)2 (5–8) with tridentate NNO Schiff base ligands GL1− and GL2− derived from 5-G-substituted salicylaldehydes (G = NO2, Br, H, Me) and the diamines 1,2-ethanediamine and 1,3-propanediamine, respectively, were investigated aiming at shedding light on possible magneto-structural correlation in this class of complexes. All derivatives contain [Cu3(μ3-OH)(L)3]2+ cations with partial cubane Cu3O4 cores, and the metal ions are linked together in a pyramidal fashion by a triple-bridging hydroxido group, giving rise to propellers with three [Cu(L)]+ blades. In these spin-frustrated magnetic systems, the three copper(II) ions within a cluster communicate anti-ferromagnetically (−2JŜi·Ŝj convention) through the bridging OH group with coupling constants J ranging from −4.5(1) for 4 (G = Me) to −10.1(1) cm−1 for 1 (G = NO2), and stabilization of the doublet S = 1/2 ground state. The structural features of the complexes reveal very minimal deviations upon variation of G or the diamine flexibility along the whole series of compounds, preserving almost constant magnetic cores. Similar conclusions are also drawn by DFT gas-phase geometry optimizations of the [Cu3(μ3-OH)(L)3]2+ cations. Therefore, confident of excluding structural influences on the magnetic super-exchange path, the modulating factor of J in our derivatives can be sought after the different electronic demand of G. Atomic NBO charges support this point, revealing small but systematic variations in the electron density flow along the blades and the positive charge on copper(II) ions with the electronic nature of G, with the most remarkable effect given by the nitro group. Topological analysis of electron density according to the Quantum Theory of Atoms In Molecules further support the distinguishing role of this group with respect to the other substituents taken into consideration, besides providing indirect information about the super-exchange path.