Covalency Effects Research Articles

Derivation of Lanthanide Series Crystal Field Parameters From First Principles.

Two series of lanthanide complexes have been chosen to analyze trends in the magnetic properties and crystal field parameters (CFPs) along the two series: The highly symmetric LnZn16 (picHA)16 series (Ln=Tb, Dy, Ho, Er, Yb; picHA=picolinohydroxamic acid) and the [Ln(dpa)3 ](C3 H5 N2 )3 ⋅3H2 O series (Ln=Ce-Yb; dpa=2,6-dipicolinic acid) with approximate three-fold symmetry. The first series presents a compressed coordination sphere of eight oxygen atoms whereas in the second series, the coordination sphere consists of an elongated coordination sphere formed of six oxygen atoms. The CFPs have been deduced from ab initio calculations using two methods: The AILFT (ab initio ligand field theory) method, in which the parameters are determined at the orbital level, and the ITO (irreducible tensor operator) decomposition, in which the problems are treated at the many-electron level. It has been found that the CFPs are transferable from one derivative to another, within a given series, as a first approximation. The sign of the second-order parameter differs in the two series, reflecting the different environments. It has been found that the use of the strength parameter S allows for an easy comparison between complexes. Furthermore, in both series, the parameters have been found to decrease in magnitude along the series, and this decrease is attributed to covalent effects.

The nature of the chemical bond in UO2

AbstractThe nature of the chemical bond in UO2 was analyzed taking into account the X‐ray photoelectron spectroscopy (XPS) structure parameters of the valence and core electrons, as well as the relativistic discrete variation electronic structure calculation results for this oxide. The ionic/covalent nature of the chemical bond was determined for the UO8 (D4h) cluster, reflecting uranium's close environment in UO2, and the U13O56 and U63O216 clusters, reflecting the bulk of solid uranium dioxide. The bar graph of the theoretical valence band (from 0 to ~35 eV) of XPS spectrum was built such that it was in satisfactory agreement with the experimental spectrum of a UO2 single crystalline thin film. It was shown that unlike the crystal field theory results, the covalence effects in UO2 are significant due to the strong overlap of the U 6p and U 5f atomic orbitals with the ligand orbitals, in addition to the U 6d atomic orbital (AO). A quantitative molecular orbital (MO) scheme for UO2 was built. The contribution of the MO electrons to the chemical bond covalence component was evaluated on the basis of the bond population values. It was found that the electrons of inner valence molecular orbitals (IVMO) weaken the chemical bond formed by the electrons of outer valence molecular orbitals (OVMO) by 32% in UO8 and by 25% in U63O216.

Coaxial sensing bio-amplifier for ultrasensitive detections of circulating tumor DNAs

We herein report the first attempt to engineer a coaxial-sensing 3D amplifier able to achieve dynamic self-assembly in response to a mutated-ctDNA target. A bio-nanofiber is firstly manufactured via an ingenious double-channel electrostatic spinning and DNA rolling circle replication (RCR) technology, which offered an ideal scaffold for assembly of 3D amplifier activated by target recognition. The coaxial-controllable signal amplifier presented several advantages. (1) Given its “coaxial sensing effect”, the proposed bio-amplifier played the coaxial transduction for signal enrichment to vastly increase sensitivity, capable of discriminating a single-base mismatched sequence from the perfectly complementary one, using ctDNA-134A as a model analyte. (2) Due to “covalent bridges lock effect” in an identifying chip with locked nucleic acid beacons, this 3D amplifier expressed high specificity and biostability toward seven different mutated-ctDNAs. (3) Profiting from special configuration of bioactive nanofibers and DNA replication programming, this catalytic bio-amplifier possessed “signal enrichment effect”, which enhanced dynamic range toward ctDNA-134A detection and hybridized without any external indicators. This innovative bio-amplifier has a detection limit of 5.1 aM for ctDNA-134A with superior specificity, excellent sensitivity, and good performance. This pioneered method was further applied for broadly differentiate cells and evaluate changes in the expression levels of intracellular mutated-ctDNAs.

Ab initio simulations of the atomic and electronic environment around B in Fe–Nb–B metallic glasses

By using ab initio molecular dynamical simulation, the local atomic and electronic environment around B atoms in ternary Fe–Nb–B alloys was investigated in details. We find that, with a large amount of B addition, abundant direct B–B bonds promote the propagation of prisms-like B-centered <0 3 6 0> polyhedron instead of antiprisms-like <0 2 8 0> polyhedron in Fe–Nb–B system. <0 3 6 0> polyhedron has a similar atomic configuration as the only B-centered <0 5 4 0> polyhedron in metastable Fe23B6 phase. It causes that the Fe23B6 phase rather than simple bcc α-Fe phase forms as the primary crystallization phase in Fe-rich system via the direct B–B bonding. Such a strong B–B covalent bonding as indicated by an obvious pseudogap in the density of states of p-orbital of B in the vicinity of Fermi level and the high charge density distribution between B–B bonds, also benefits the formation of skeleton networks by the vertex, edge and face sharing of <0 5 4 0> polyhedra in Fe23B6 phase. These complex crystallization modes and directional bonding structures introduced by the covalent effect of metalloid B are the structural origin for the excellent glass-forming ability of B-rich systems. In addition, the B alloying also enhances the average magnetic moments of Fe. However, the negative spin polarization of both Nb and B eventually causes a worse magnetism. Thus, for maintaining a high magnetic performance and formability in Fe–Nb–B system, the proper metalloid addition should be considered for material design. Our studies help us better understand the structural origin for the formation of metallic glass and offer a potential strategy for designing ferromagnetic glassy alloys with the outstanding formability as well as magnetism.

A uniform research on the optical and EPR spectral data for the trigonal Cr3+ center in Cr3+-doped Ca3Ga2Ge3O12 garnet

This article represents a uniform calculation for the optical and electron paramagnetic resonance (EPR) spectral data of the trigonal Cr3+ center in Cr3+-doped Ca3Ga2Ge3O12 (CGGG) garnet crystal by using the full diagonalization (of energy matrix) method. The method is built on the two-spin-orbit-parameter model where the contributions due to both the spin-orbit parameter of central dn ion in the traditional crystal-field theory and that of ligand ion via covalence effect are comprised. The calculated results indicate that the observed ten optical and EPR data (seven optical bands and three EPR parameters g//, g⊥, D) can be rationally interpreted by this method with only four adjustable parameters. The crystal field parameters applied in the calculation are evaluated by the superposition model, which leads the defect structure of Cr3+ center in CGGG: Cr3+ crystal to be determined. The outcomes are discussed.

Covalent bonds-integrated graphene foam with superb electromechanical properties as elastic conductor and compressive sensor

Constructing highly conductive and mechanically robust graphene foams remains a great challenge for practical applications. Herein, we report a facile fabrication of covalently cross-linked graphene foam (CCGF) by CN bonds with superb electromechanical properties. Benefiting from covalent bonds-enhanced effect and removal of oxygen-containing groups of GO sheets, the resulting CCGFs exhibit an excellent compressibility and conductivity. More importantly, the CCGFs exhibit tunable conductivity at different compressed strains and ultrasensitive stress responsivity (0.046 kPa−1 in the regime of 3.5–5 kPa), featuring huge prospects for elastic conductive and ultrasensitive sensing applications. The proposed strategy may enlighten the fabrication of novel materials via cross-linking for other related applications.

Emergence of the structure-directing role of f-orbital overlap-driven covalency

FEUDAL (f’s essentially unaffected, d’s accommodate ligands) is a longstanding bonding model in actinide chemistry, in which metal-ligand binding uses 6d-orbitals, with the 5f remaining non-bonding. The inverse-trans-influence (ITI) is a case where the model may break down, and it has been suggested that ionic and covalent effects work synergistically in the ITI. Here, we report an experimentally grounded computational study that quantitatively explores the ITI, and in particular the structure-directing role of f-orbital covalency. Strong donor ligands generate a cis-ligand-directing electrostatic potential (ESP) at the metal centre. When f-orbital participation, via overlap-driven covalency, becomes dominant via short actinide-element distances, this ionic ESP effect is overcome, favouring a trans-ligand-directed geometry. This study contradicts the accepted ITI paradigm in that here ionic and covalent effects work against each other, and suggests a clearly non-FEUDAL, structure-directing role for the f-orbitals.

Theoretical investigation on the optical and EPR spectra for Cu2+ -doped ZnO-CdS nanocomposites.

The three optical absorption bands and EPR parameters of the [CuO6 ]10- center in the ZnO-CdS composite nanopowders are theoretically studied from the perturbation formulas based on the cluster approach. In the formulas, the contributions to EPR parameters arising from the ligand orbital and spin-orbit coupling interactions via covalence effect are considered. For the studied [CuO6 ]10- cluster, the Cu-O bond lengths are suggested to show a relative elongation ratio ρ (≈ 4.1%) along the z-axis due to Jahn-Teller effect. The defect models suggested in this work are different from the previous assumption that the impurity Cu2+ can replace the host Zn2+ site when it enters the lattices of the ΖnO and ΖnS nanocrystals, forming the tetrahedral [CuΧ4 ]6- clusters (Χ=O, S). The validity of the proposed model is discussed. The differences between the present calculations and the previous ones for the interstitial Cu2+ center in ZnO nanocrystals are analyzed in view of the dissimilar impurity behaviors due to the new composition CdS and distinct preparation conditions.

Electrostatic interactions and covalent binding effects on the energy transfer between quantum dots and reaction centers of purple bacteria

The effect of electrostatic interaction and covalent binding on the energy transfer from negatively charged CdSe/CdS/ZnS-COО− and positively charged CdSe/CdS/ZnS-N H3+ quantum dots to reaction centers of Rb. sphaeroides bacteria (RC) in aqueous solutions is reported. The study was performed using optical absorption and steady-state and time resolved luminescence spectroscopies. The experiments were accompanied by theoretic modelling of charge distribution on the RC surface. More effective energy transfer from positively charged QD to RC, as compared with negatively charged QD, was observed. This effect was associated with the different localization of positively and negatively charged QD on the RC surface. The theoretic analysis has demonstrated that the periplasmic RC side is characterized by larger negative charge density as compared with the cytoplasmic side. Therefore, positively charged QD are localized mainly on periplasmic RC side while negatively charged QD are localized on the cytoplasmic RC side. In RC energy acceptors (porphyrins) are localized closer to the periplasmic side. Therefore, the energy transfer efficiency from positively charged QD is higher. The increase in ionic strength equalizes the charge distribution on both RC sides, thus levelling affinity of differently charged QD with RC. Equal energy transfer efficiency for both covalently bound and unbound QD is due to the fact of QD localization on the same RC side. This study demonstrates that for binding of charged QD with RC the electrostatic interaction is principal.

Vibrational Control of Covalency Effects Related to the Active Sites of Molybdenum Enzymes.

A multitechnique spectroscopic and theoretical study of the Cp2M(benzenedithiolato) (M = Ti, V, Mo; Cp = η5-C5H5) series provides deep insight into dithiolene electronic structure contributions to electron transfer reactivity and reduction potential modulation in pyranopterin molybdenum enzymes. This work explains the magnitude of the dithiolene folding distortion and the concomitant changes in metal-ligand covalency that are sensitive to electronic structure changes as a function of d-electron occupancy in the redox orbital. It is shown that the large fold angle differences correlate with covalency, and the fold angle distortion is due to a pseudo-Jahn-Teller (PJT) effect. The PJT effect in these and related transition metal dithiolene systems arises from the small energy differences between metal and sulfur valence molecular orbitals, which uniquely poise these systems for dramatic geometric and electronic structure changes as the oxidation state changes. Herein, we have used a combination of resonance Raman, magnetic circular dichroism, electron paramagnetic resonance, and UV photoelectron spectroscopies to explore the electronic states involved in the vibronic coupling mechanism. Comparison between the UV photoelectron spectroscopy (UPS) of the d2 M = Mo complex and the resonance Raman spectra of the d1 M = V complex reveals the power of this combined spectroscopic approach. Here, we observe that the UPS spectrum of Cp2Mo(bdt) contains an intriguing vibronic progession that is dominated by a "missing-mode" that is composed of PJT-active distortions. We discuss the relationship of the PJT distortions to facile electron transfer in molybdenum enzymes.

Free-Standing Sandwich-Type Graphene/Nanocellulose/Silicon Laminar Anode for Flexible Rechargeable Lithium Ion Batteries.

Freely deformable and free-standing electrodes together with high capacity are crucial to realizing flexible Li-ion batteries. Herein, a lamellar graphene/nanocellulose/silicon (GN/NC/Si) film assembled by interpenetrated GN nanosheets is synthesized via a facile vacuum-assisted filtration approach accompanied by the covalent cross-linking effect of glutaraldehyde. The hybrid film consists of the highly conductive GN matrix as an effective current collector, hydroxylated silicon nanoparticles (Si NPs) embedded uniformly within GN interlayer and NC as adhesive to cross-link GN and Si NPs. When applied as anode, the GN/NC/Si film exhibits a high reversible capacity of 1251 mA h g-1 at 100 mA g-1 after 100 cycles and superior rate capability. More importantly, in the stress-strain test, this film represents robust mechanical strength, which not only provides good flexibility but also accommodates volume change of Si during cycling. By coupling with lithium cobalt oxide as the cathode, the full cell successfully powers a light-emitting diode, even bended and folded, indicating the deformation-tolerant GN/NC/Si film electrode for flexible Li-ion batteries. Therefore, the design of layered nanocomposites will offer the possibility closer to the application of flexible batteries.

Nature of Lone-Pair–Surface Bonds and Their Scaling Relations

We investigate the (surface) bonding of a class of industrially and biologically important molecules in which the chemically active orbital is a 2 p electron lone pair located on an N or O atom bound via single bonds to H or alkyl groups. This class includes water, ammonia, alcohols, ethers, and amines. Using extensive density functional theory (DFT) calculations, we discover scaling relations (correlations) among molecular binding energies of different members of this class: the bonding energetics of a single member can be used as a descriptor for other members. We investigate the bonding mechanism for a representative (H2O) and find the most important physical surface properties that dictate the strength and nature of the bonding through a combination of covalent and noncovalent electrostatic effects. We describe the importance of surface intrinsic electrostatic, geometric, and mechanical properties in determining the extent of the lone-pair-surface interactions. We study systems including ionic materials in which the surface positive and negative centers create strong local surface electric fields, which polarize the dangling lone pair and lead to a strong "electrostatically driven bond". We emphasize the importance of noncovalent electrostatic effects and discuss why a fully covalent picture, common in the current first-principles literature on surface bonding of these molecules, is not adequate to correctly describe the bonding mechanism and energy trends. By pointing out a completely different mechanism (charge transfer) as the major factor for binding N- and O-containing unsaturated (radical) adsorbates, we explain why their binding energies can be tuned independently from those of the aforementioned species, having potential implications in scaling-driven catalyst discovery.

Investigation of anisotropic mechanical properties of textured KSr2Nb5O15 ceramics via ab‐initio calculation and nanoindentation

AbstractAnisotropic mechanical properties of KSr2Nb5O15 (KSN) crystals were investigated through first‐principles calculations based on density functional theory. These properties were experimentally verified via nanoindentation on textured KSN ceramics fabricated, using a reactive template grain growth method. Nanoindentation was performed in directions parallel and perpendicular to the [001] direction of samples consisting of highly oriented grains with tetragonal symmetry. Calculations revealed that Nb‐O yields a relatively strong covalent effect and Nb‐O octahedral distortions induce spontaneous polarization in the KSN crystal. The measured indentation modulus values concurred with the predictions, based on the calculated elastic constants, as indicated by an anisotropic ratio of ~10% between the 2 tested orientations. The hardness exhibited negligible anisotropy. However, the predictions revealed a pronounced anisotropy of the Young's modulus (ratio of ~40% between the [100] direction and a direction tilted by ~45° from the [001] toward the [100]).

8-Layer Shifted Hexagonal Perovskite Ba8MnNb6O24: Long-Range Ordering of High-Spin d5 Mn2+ Layers and Electronic Structure.

A new 8-layer shifted hexagonal perovskite Ba8MnNb6O24 has been synthesized in air, featuring unusual long-range B-cation ordering with single octahedral high-spin d5 Mn2+ layers separated by ∼1.9 nm within the corner-sharing octahedral d0 Nb5+ host, analogous to Ba8(Zn/Co)Nb6O24. The large size and charge differences between high-spin Mn2+ and Nb5+, as well as the out-of-center distortion of NbO6 octahedra associated with the bonding covalence and second-order Jahn-Teller effect of Nb5+, drive long-range cationic ordering, thus stabilizing Ba8MnNb6O24. The Ba8MnNb6O24 pellet exhibits a high dielectric permittivity, εr ∼ 38, and a large temperature coefficient of resonant frequency, τf ∼ 20 ppm/K, but a dielectric loss ( Qf ∼ 987 GHz) and conductivity (∼10-8-10-3 S/cm within 473-1173 K) much higher than those of Ba8ZnNb6O24. Electronic structures from density functional theory calculations reveal that Ba8MnNb6O24 is a Mott insulator in contrast with the charge-transfer insulator nature of Ba8ZnNb6O24, and they confirm that the off-center distortion of Nb5+ contributes to stabilization of the 8-layer ordered shifted structure. The contrast between conductivity and dielectric loss of Ba8MnNb6O24 and Ba8ZnNb6O24 is understood based on the electronic structure that depends on high-spin d5 Mn2+ and d10 Zn2+ cations. The hopping of 3d valence electrons in high-spin Mn2+ to Nb5+ 4d conduction bands over a small gap (∼2.0 eV) makes Ba8MnNb6O24 more conductive than Ba8ZnNb6O24, where the electrons are conducted via the hopping of a lattice O 2p valence electron to the Nb5+ 4d conduction bands over a larger gap (∼3.9 eV). The high microwave dielectric loss of BMN may be mainly ascribed to the half-filled Mn 3d orbits, which is understood based on the softened infrared modes that increase the lattice vibration anharmonicity as well as the resonant spin excitation of unpaired d electrons.

Surface Attachment of Natural Antimicrobial Coatings onto Conventional Polypropylene Nonwoven Fabric and Its Antimicrobial Performance Assessment

The growing number of microbial cross-contamination events necessitates the development of novel antimicrobial strategies in the food industry. In this study, a polypropylene nonwoven fabric (PPNWF) was grafted with a natural antimicrobial component, aloe emodin (AE), and its antimicrobial performance was evaluated. The grafted samples (PPNWF-g-AE) were examined using Fourier transform infrared spectroscopy and scanning electron microscopy. AE was effectively grafted onto the surface of the PPNWF through the adsorption covalent effect. Compared with nongrafted PPNWF, the antimicrobial activity of PPNWF-g-AE against Staphylococcus aureus, Escherichia coli, and Candida albicans was significantly enhanced. Scanning electron micrographs confirmed that the inhibitory mechanism of PPNWF-g-AE was the microbicidal function of the grafted AE. These findings indicate that PPNWF-g-AE has potential as an effective antimicrobial material in food applications.

Trigonal Distortions of the Cr3+ Octahedral Centers in Cr3+-Doped ABO3 (A = Sc, In, Lu) Crystals Obtained by Analyzing EPR Data

The spin-Hamiltonian parameters (g factors g//, g⊥ and zero-field splitting D) of the trigonal Cr3+ centers in Cr3+-doped ABO3 (A = Sc, In, Lu) borate crystals are computed from both the complete diagonalization (of energy matrix) method and also the perturbation method based on the two-spin–orbit-parameter model, where the contributions to spin-Hamiltonian parameters due to both the spin–orbit parameter of central d n ion and that of ligands via covalence effect are considered. The calculated results are compatible with those available in experiments. The defect structures of the trigonal (CrO6)9− octahedral centers are also evaluated from the calculations. It is found that the trigonal (MO6)9− octahedra change from the elongation in the host crystals to the compression in the impurity centers because of the large size and nature mismatch substitution in these Cr3+-doped ABO3 crystals. The results are discussed.

Covalency and spin-orbit coupling driven magnetism in the double-perovskite iridates Sr2MIrO6 ( M=Ca , Mg)

We have investigated the effect of spin-orbit coupling (SOC) and strong covalency on the magnetism of double-perovskite iridates (${\mathrm{Sr}}_{2}{M\mathrm{IrO}}_{6}$, $M=\mathrm{Ca}$, Mg) using first principles as well as model Hamiltonian calculations. Our calculation shows that strong Ir-$d$ and O-$p$ covalency in these double-perovskite iridates results in the deviation from the expected $6+$ charge state of Ir, leading to an unquenched orbital moment in the presence of SOC. We have studied in detail the nature of magnetism and our calculations of isotropic exchange interactions for these double-perovskite iridates suggest the systems to be frustrated. We argue that the SOC driven easy plane anisotropy possibly promotes long range magnetic order suggested for these systems indicating the importance of SOC in both these systems. Further, our model calculation considering ideal ${d}^{3}$ electronic configuration for Ir emphasizes the role of SOC, noncubic crystal field and Ir-Ir hopping in the reduction of the spin moment.

Soft x-ray absorption spectroscopy study of the electronic structures of the MnFe Prussian blue analogs (RbxBay)Mn[3−(x+2y)]/2[Fe(CN)6]H2O

The electronic structures of Prussian blue analog $({\mathrm{Rb}}_{x}{\mathrm{Ba}}_{y}){\mathrm{Mn}}_{[3\ensuremath{-}(x+2y)]/2}[\mathrm{Fe}{(\mathrm{CN})}_{6}]$ cyanides have been investigated by employing soft x-ray absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD) at the Fe and Mn $L$ $(2p)$ edges. The measured XAS spectra have been analyzed with the configuration-interaction (CI) cluster model calculations. The valence states of the Fe and Mn ions are found to be ${\mathrm{Fe}}^{2+}\text{\ensuremath{-}}{\mathrm{Fe}}^{3+}$ mixed valent, with an average valency of $v(\mathrm{Fe})\ensuremath{\sim}2.8$ and nearly divalent $({\mathrm{Mn}}^{2+})$, respectively. Our Mn/Fe $2p$ XMCD study supports that ${\mathrm{Mn}}^{2+}$ ions are in the high-spin states while ${\mathrm{Fe}}^{2+}\text{\ensuremath{-}}{\mathrm{Fe}}^{3+}$ ions are in the low-spin states. The Fe and Mn $2p$ XAS spectra are found to be essentially the same for $80\ensuremath{\le}T\ensuremath{\le}300$ K, suggesting that a simple charge transfer upon cooling from ${\mathrm{Fe}}^{3+}\text{\ensuremath{-}}\mathrm{CN}\text{\ensuremath{-}}{\mathrm{Mn}}^{2+}$ to ${\mathrm{Fe}}^{2+}\text{\ensuremath{-}}\mathrm{CN}\text{\ensuremath{-}}{\mathrm{Mn}}^{3+}$ does not occur in $({\mathrm{Rb}}_{x}{\mathrm{Ba}}_{y}){\mathrm{Mn}}_{[3\ensuremath{-}(x+2y)]/2}[\mathrm{Fe}{(\mathrm{CN})}_{6}]$. According to the CI cluster model analysis, it is necessary to take into account both the ligand-to-metal charge transfer and the metal-to-ligand charge transfer in describing Fe $2p$ XAS, while the effect of charge transfer is negligible in describing Mn $2p$ XAS. The CI cluster model analysis also shows that the trivalent ${\mathrm{Fe}}^{3+}$ ions have a strong covalent bonding with the $\mathrm{C}\ensuremath{\equiv}\mathrm{N}$ ligands and are under a large crystal-field energy of $10Dq\ensuremath{\sim}3$ eV, in contrast to the weak covalency effect and a small $10Dq\ensuremath{\sim}0.6$ eV for the divalent ${\mathrm{Mn}}^{2+}$ ions.

Perovskite-Type InCoO3 with Low-Spin Co3+: Effect of In-O Covalency on Structural Stabilization in Comparison with Rare-Earth Series.

Perovskite rare-earth cobaltites ACoO3 (A = Sc, Y, La-Lu) have been of enduring interest for decades due to their unusual structural and physical properties associated with the spin-state transitions of low-spin Co3+ ions. Herein, we have synthesized a non-rare-earth perovskite cobaltite, InCoO3, at 15 GPa and 1400 °C and investigated its crystal structure and magnetic ground state. Under the same high-pressure and high-temperature conditions, we also prepared a perovskite-type ScCoO3 with an improved cation stoichiometry in comparison to that in a previous study, where synthesis at 6 GPa and 1297 °C yielded a perovskite cobaltite with cation mixing on the A-site, (Sc0.95Co0.05)CoO3. The two perovskite phases have nearly stoichiometric cation compositions, crystallizing in the orthorhombic Pnma space group. In the present investigation, comprehensive studies on newly developed and well-known Pnma ACoO3 perovskites (A = In, Sc, Y, Pr-Lu) show that InCoO3 does not fulfill the general evolution of crystal metrics with A-site cation size, indicating that InCoO3 and rare-earth counterparts have different chemistry for stabilizing the Pnma structures. Detailed structural analyses combined with first-principles calculations reveal that the origin of the anomaly for InCoO3 is ascribed to the A-site cation displacements that accompany octahedral tilts; despite the highly tilted CoO6 network, the In-O covalency makes In3+ ions reluctant to move from their ideal cubic-symmetry position, leading to less orthorhombic distortion than would be expected from electrostatic/ionic size mismatch effects. Magnetic studies demonstrate that InCoO3 and ScCoO3 are diamagnetic with a low-spin state of Co3+ below 300 K, in contrast to the case of (Sc0.95Co0.05)CoO3, where the high-spin Co3+ ions on the A-site generate a large paramagnetic moment. The present work extends the accessible composition range of the low-spin orthocobaltite series and thus should help to establish a more comprehensive understanding of the structure-property relation.

Magnetic Anisotropy from Main-Group Elements: Halides versus Group 14 Elements.

Precise modulation of the magnetic anisotropy of a transition-metal center would affect physical properties ranging from photoluminescence to magnetism. Over the past decade, exerting nuanced control over ligand fields enabled the incorporation of significant magnetic anisotropy in a number of mononuclear transition-metal complexes. An alternate approach to increasing spin-orbit coupling relies upon using heavy diamagnetic main-group elements as sources of magnetic anisotropy. Interacting first-row transition metals with main-group elements enables the transfer of magnetic anisotropy to the paramagnetic metal center without restricting coordination geometry. We sought to study the effect of covalency on this anisotropy transfer by probing the effect of halides in comparison to early main-group elements. Toward that end, we synthesized a series of four isostructural heterobimetallic complexes, with germanium or tin covalently bound to a triplet spin Fe(II) center. These complexes are ligated by a halide (Br- or I-) in the apical position to yield a series of complexes with variation in the mass of the main-group elements. This series enabled us to interrogate which electronic structure factors influence the heavy-atom effect. Using a suite of approaches including magnetometry, computation, and Mössbauer spectroscopy, we probed the electronic structure and the spin-orbit coupling, as parametrized by axial zero-field splitting across the series of complexes, and found an increase in zero-field splitting from -11.8 to -17.9 cm-1 by increasing the axial ligand mass. Through direct comparison between halides and group 14 elements, we observe a greater impact on magnetic anisotropy from the halide interaction. We attribute this counterintuitive effect to a larger spin population on the halide elements, despite greater covalency in the group 14 interactions. These results recommend modification of the intuitive design principle of increasing covalency toward a deeper focus on the interactions of the spin-bearing orbitals.