Strong Antiferromagnetic Coupling Research Articles

Thermoelectric Performance in Triplet‐Ground‐State Polymer Intrinsically Boosted by Enhanced Proquinoidal Characteristic

AbstractOver the past decade, polymer thermoelectric materials featuring flexibility, lightness, and bio‐friendliness have been paid increasing attention as promising candidates for waste heat recovery and energy generation. For a long time, the dominant approach to optimizing the thermoelectric performance of most organic materials is chemical doping, which, however, is not always ideal for practical applications due to its tendency to involve intricate processing procedure and trigger material and device instability. Currently, the pursuit of single‐component neutral thermoelectric materials without exogenous doping presents a compelling alternative. In this work, we designed and synthesized a high‐spin polymer material, PBBT‐TT, by simultaneously employing thieno[3,4‐b]thiophene (TbT) and benzo[1,2‐c : 4,5‐c′]bis[1,2,5]thiadiazole (BBT) units with pronounced proquinoidal characteristics, its analogue, PBBT‐T to demonstrate the effect of the TbT unit was also synthesized. The results indicate that because of the enhanced quinoidal resonance, increased spin density and strong intermolecular antiferromagnetic coupling, PBBT‐TT exhibits high intrinsic electrical conductivity and Seebeck coefficient, which showcases an outstanding power factor of 26.1 μW m−1 K−2 without doping. This achievement surpasses other neutral organic conjugated polymer and radical conductors, and is even comparable to some typical early‐stage doped polymers. Notably, PBBT‐TT exhibits remarkable ambient stability, retaining its initial thermoelectric performance over a 120‐day period. Our finding demonstrates that modulating the intermolecular spin interactions in open‐shell polymers through the introduction of strong proquinoidal units is an effective strategy for the development of doping‐free, intrinsically high‐performance polymer thermoelectric materials.

Thermoelectric Performance in Triplet-Ground-State Polymer Intrinsically Boosted by Enhanced Proquinoidal Characteristic.

Over the past decade, polymer thermoelectric materials featuring flexibility, lightness, and bio-friendliness have been paid increasing attention as promising candidates for waste heat recovery and energy generation. For a long time, the dominant approach to optimizing the thermoelectric performance of most organic materials is chemical doping, which, however, is not always ideal for practical applications due to its tendency to involve intricate processing procedure and trigger material and device instability. Currently, the pursuit of single-component neutral thermoelectric materials without exogenous doping presents a compelling alternative. In this work, we designed and synthesized a high-spin polymer material, PBBT-TT, by simultaneously employing thieno[3,4-b]thiophene (TbT) and benzo[1,2-c : 4,5-c']bis[1,2,5]thiadiazole (BBT) units with pronounced proquinoidal characteristics, its analogue, PBBT-T to demonstrate the effect of the TbT unit was also synthesized. The results indicate that because of the enhanced quinoidal resonance, increased spin density and strong intermolecular antiferromagnetic coupling, PBBT-TT exhibits high intrinsic electrical conductivity and Seebeck coefficient, which showcases an outstanding power factor of 26.1 μW m-1 K-2 without doping. This achievement surpasses other neutral organic conjugated polymer and radical conductors, and is even comparable to some typical early-stage doped polymers. Notably, PBBT-TT exhibits remarkable ambient stability, retaining its initial thermoelectric performance over a 120-day period. Our finding demonstrates that modulating the intermolecular spin interactions in open-shell polymers through the introduction of strong proquinoidal units is an effective strategy for the development of doping-free, intrinsically high-performance polymer thermoelectric materials.

{Fe3} to {Fe6} clusters through changing flexible 1,3-propanediol to rigid ethylene glycol: Syntheses, structures and magnetic properties

Two related FeIII complexes [Fe3(μ3-O)(O2CPh)6(H2L1)2(H2O)](NO3)·2C3H8O2 (1 {Fe3}) and [Fe6(μ3-O)2(O2CPh)6(HL2)6](NO3)2·2CH3CN (2 {Fe6}) (H2L1 = 1,3-propanediol and H2L2 = ethylene glycol) were synthesized and characterized. Complex 1 consists of a [Fe3O(PhCO2)3] unit. Changing ethylene glycol to 1,3-propanediol, the final cluster 2 comprises two [Fe3O(PhCO2)3] triangular units connected by six mono-deprotonated μ2−1η:2η ethylene glycol. The result indicates that the syntheses of FeIII complexes is sensitive to the ligands. Variable-temperature (T) and field (B) solid-state direct current magnetization (M) studies show that complexes 1 and 2 show strong anti-ferromagnetic coupling between FeIII ions, resulting in ground-state spins of S = 1/2 for 1 and S = 0 for 2, which is also confirmed by the calculations.

Binuclear Coordination Assemblies of Metal Tetraphenylporphyrins (M = Mn, Fe, and In) with Anionic Thioindigo Bridges as Promising Magnetic Systems with Tunable Properties.

A series of hybrids comprising two metal (Mn, Fe, and In) tetraphenylporphyrins axially substituted with anionic bidentate trans-thioindigo ligands (TI) were obtained. Substitution of the axial chloride anion by an oxygen atom of the dye forms short M-O bonds. Crystalline binuclear assemblies (TI•-)·{[MnIITPP]0·[MnIIITPP]+}·xC6H4Cl2 (x = 2 for 1 or 1 for 2) and (TI2-){[MIIITPP]+}2·xC6H4Cl2 (M = Fe and x = 2 for 3, M = In and x = 1 for 4) were synthesized. The thioindigo (TI2-) dianion and metal (FeIII and InIII) atoms in TPPs maintain their initial charge states during the formation of 3 and 4, allowing the separation of paramagnetic FeIII or diamagnetic InIII ions by a diamagnetic TI2- bridge. Strong antiferromagnetic coupling is observed between FeIII (S = 5/2) centers in complex 3. Partial reduction of MnIII to MnII occurs upon the formation of 1 and 2, leading to assemblies containing three paramagnetic centers: MnII (S = 5/2), MnIII (S = 2), and TI•- radical anion (S = 1/2). Orthogonal arrangement of TPP and TI molecules in 1 provides strong ferromagnetic coupling. Weak antiferromagnetic coupling is realized in 2 due to the rotation of the TI bridge.

Enhancement of interlayer exchange coupling via intercalation in 2D magnetic bilayers: towards high Curie temperature.

Two-dimensional magnetic materials are considered as promising candidates for developing next-generation spintronic devices by providing the possibility of scaling down to nanometers. However, a low Curie temperature is a crucial problem for practical applications, being intimately related to weak interlayer exchange coupling. Here, by using density functional theory calculations, we show that interlayer exchange coupling can be enhanced by intercalating 3d transition metals (Sc to Zn) into a bilayer of CrI3 and NiI2. It is found that intercalated Ni and Cr atoms exhibit strong antiferromagnetic coupling with the CrI3 and NiI2 host layers, respectively. This enhances the ferromagnetic interlayer exchange coupling between the host layers by many folds compared to pristine CrI3 and NiI2 bilayers. Moreover, both intercalated compounds show out-of-plane magnetic anisotropy with half metallic nature, which makes them ideal candidates for spintronics applications. Thereby our work provides a rational approach to raise the Curie temperature of non-metallic two-dimensional magnets by intercalation.

Understanding the nature of the magnetic coupling in transition metal doped Bi2Se3

In this paper, we employ electronic structure theory to investigate the nature of the exchange coupling in transition metal doped Bi2Se3. We focus on V, Cr, Mn, and Fe, which have been under scrutiny for the realization of the quantum anomalous Hall effect. For simplicity, we model the doping process as happening inside a single layer of Bi within a single quintuple layer inside a three-formula-unit conventional hexagonal cell and consider situations of full coverage or half coverage. Due to the covalent nature of the chemical bond between transition metal atoms and selenium, this simple model is capable of describing the fundamental features of the intraplane exchange coupling, while offering a clearer analysis of the response to structural, magnetic, and electronic perturbations. In agreement with recent literature, our results confirm that the van Vleck mechanism has a very marginal contribution to the exchange coupling. Depending on the filling of the 3d shell and on the details of the electronic structure, several other mechanisms compete and cooperate to induce the magnetic order. For V, double exchange and superexchange cooperate to have the strongest ferromagnetic coupling among the investigated elements, followed by Cr where only superexchange is active. For Mn, superexchange and double exchange compete to create an extremely weak ferromagnetic order. For Fe, a strong antiferromagnetic coupling caused by the double exchange is observed to dominate over the ferromagnetic Ruderman-Kittel-Kasuya-Yosida interaction, but the high sensitivity of this competition to the doping concentration suggests that our conclusion may not hold in the dilute limit. Overall, Fe doping seems to offer the most intriguing competition of exchange mechanisms that can be tuned by adjusting the doping concentration and the details of the host, as, e.g., by replacing Se with Te or Bi with Sb. Published by the American Physical Society 2024

Quantum magnetism in Fe2Cu2 polymeric branched chains: insights from exactly solved Ising-Heisenberg model

The spin-1/2 Ising-Heisenberg branched chain, inspired by the magnetic structure of three isostructural polymeric coordination compounds [(Tp)2Fe2(CN)6X (bdmap)Cu2(H2O)] ⋅ H2O to be further denoted as Fe2Cu2 (Tp = tris(pyrazolyl)hydroborate, bdmapH = 1,3-bis(dimethylamino)-2-propanol, HX = acetic acid, propionic acid or trifluoroacetic acid), is rigorously studied using the transfer-matrix method. The overall ground-state phase diagram reveals three distinct phases: a quantum antiferromagnetic phase, a quantum ferrimagnetic phase and a classical ferromagnetic phase. In the zero-temperature magnetization curve, two quantum ground states are manifested as intermediate plateaus at zero and half of the saturation magnetization, while the magnetization reaches its saturated value within the classical ferromagnetic phase. The bipartite entanglement between nearest-neighbor Heisenberg spins is more pronounced in the quantum ferrimagnetic phase compared to the quantum antiferromagnetic phase due to a fully polarized nature of the Ising spins. A reasonable agreement between theoretical predictions for the spin-1/2 Ising-Heisenberg branched chain and experimental data measured for a temperature dependence of the magnetic susceptibility and a low-temperature magnetization curve suggests strong antiferromagnetic coupling between nearest-neighbor Cu2+-Cu2+ magnetic ions and moderately strong ferromagnetic coupling between nearest-neighbor Cu2+-Fe3+ magnetic ions in the polymeric compounds Fe2Cu2. A thermal entanglement between nearest-neighbor Cu2+-Cu2+ magnetic ions persists up to a relatively high threshold temperature T ≈ 224 K and undergoes a transient magnetic-field-driven strengthening.

Short Didysprosium Covalent Bond Enables High Magnetization Blocking Temperature of a Direct 4f-4f Coupled Dinuclear Single-Molecule Magnet.

Coupling two magnetic anisotropic lanthanide ions via a direct covalent bond is an effective way to realize high magnetization blocking temperature of single-molecule magnets (SMMs) by suppressing quantum tunneling of magnetization (QTM), whereas so far only single-electron lanthanide-lanthanide bonds with relatively large bond distances are stabilized in which coupling between lanthanide and the single electron dominates over weak direct 4f-4f coupling. Herein, we report for the first time synthesis of short Dy(II)-Dy(II) single bond (3.61 Å) confined inside a carbon cage in the form of an endohedral metallofullerene Dy2@C82. Such a direct Dy(II)-Dy(II) covalent bond renders a strong Dy-Dy antiferromagnetic coupling that effectively quenches QTM at zero magnetic field, thus opening up magnetic hysteresis up to 25 K using a field sweep rate of 25 Oe/s, concomitant with a high 100 s magnetization blocking temperature (TB,100s) of 27.2 K.

Cryogenic magnetocaloric effects of NaLnF4 (Ln = Gd, Tb, Dy, Ho, Er, Tm, and Yb)

Cryogenic refrigeration technology based on magnetocaloric effects plays a critical role in a variety of technological applications. In this paper, we report the cryogenic magnetocaloric effects of a series of sodium-rare earth fluoride samples (Ln = Gd, Tb, Dy, Ho, Er, Tm, Yb) synthesized by the solid-state reaction method. These compounds all crystallize in a hexagonal crystal structure. Down to 2 K, no magnetic ordering was detected, while all compounds show negative Curie–Weiss temperatures indicative of strong antiferromagnetic coupling. Magnetic fields effectively suppress the magnetic fluctuations, leading to a maximum magnetic entropy change of −56 J kg−1 K−1 in NaGdF4 at the magnetic field change from 0 to 50 kOe. These series of compounds are potentially excellent magnetic refrigerants at low temperatures.

Geometrically frustrated Gd2Ti2O7 oxide: A comprehensive exploration of structural, magnetic, and magnetocaloric properties for cryogenic magnetic cooling applications

The magnetocaloric effect (MCE) has been extensively studied in various magnetic solids, aiming to both facilitate practical applications in magnetic cooling and deepen our understanding these materials’ intrinsic properties. This study presents a systematic investigation of Gd2Ti2O7 oxide, characterized by a geometrically frustrated magnetic structure, focusing on its structural and magnetic characteristics through experimental analysis and theoretical calculations. Emphasis is placed on its magnetic phase transition (MPT) and magnetocaloric properties, scrutinizing temperatures as low as 0.4 K and magnetic fields up to 16 T. The results reveal that Gd2Ti2O7 oxide possesses a crystalline cubic pyrochlore-type structure with an antiferromagnetic (AFM) semiconductor ground state. The material undergoes a first-order MPT in low field and low-temperature regimes, transitioning to a second-order MPT above 2 K up to 16 T. Evaluation of magnetocaloric parameters, including maximum magnetic entropy change, temperature-averaged entropy change, relative cooling power, and refrigerant capacity, indicates moderate values under low magnetic field changes, while significantly large values are achievable under high magnetic field changes. This finding suggests that potential cryogenic magnetocaloric materials (MCMs) with optimal performance should exhibit low MPT temperatures induced by magnetic frustration and possess a ground state with a sufficiently large magnetic moment induced by low magnetic fields, thus avoiding excessively strong AFM coupling. This study lays the groundwork for future cryogenic MCM design and provides valuable insights into the intrinsic properties of geometrically frustrated magnetic materials.

Unusual Stabilisation of Remarkably Bent Tetra-Cationic Tetra-radical Intermolecular Fe(III) μ-Oxo Tetranuclear Complexes.

A hitherto unknown series of air stable, π-conjugated, remarkably bent tetra-cation tetra-radical intermolecular Fe(III) μ-oxo tetranuclear complex, isolated from the dication diradical diiron(III) porphyrin dimers, has been synthesised and spectroscopically characterised along with single crystal X-ray structure determination of two such molecules. These species facilitate long-range charge/radical delocalisation through the bridge across the entire tetranuclear unit manifesting an unusually intense NIR band. Assorted spin states of Fe(III) centres are stabilised within these unique tetranuclear frameworks: terminal six-coordinate iron centres stabilise the admixed intermediate spin states while the central five-coordinate iron centres stabilise the high-spin states. Variable temperature magnetic susceptibility measurements indicated strong antiferromagnetic coupling for the Fe(III)-O-Fe(III) unit while the exchange interactions between the Fe centres and the porphyrin π-cation radicals are weaker as supported both by magnetic data and DFT calculations. The nature of orbital overlap between the SOMOs of Fe(III) and π* orbital of the porphyrin was found to rationalise the observed exchange coupling, establishing such a complex magnetic exchange in this tetranuclear model with a significant bioinorganic relevance.

Unusual Stabilisation of Remarkably Bent Tetra‐Cationic Tetra‐radical Intermolecular Fe(III) μ‐Oxo Tetranuclear Complexes

AbstractA hitherto unknown series of air stable, π‐conjugated, remarkably bent tetra‐cation tetra‐radical intermolecular Fe(III) μ‐oxo tetranuclear complex, isolated from the dication diradical diiron(III) porphyrin dimers, has been synthesised and spectroscopically characterised along with single crystal X‐ray structure determination of two such molecules. These species facilitate long‐range charge/radical delocalisation through the bridge across the entire tetranuclear unit manifesting an unusually intense NIR band. Assorted spin states of Fe(III) centres are stabilised within these unique tetranuclear frameworks: terminal six‐coordinate iron centres stabilise the admixed intermediate spin states while the central five‐coordinate iron centres stabilise the high‐spin states. Variable temperature magnetic susceptibility measurements indicated strong antiferromagnetic coupling for the Fe(III)−O−Fe(III) unit while the exchange interactions between the Fe centres and the porphyrin π‐cation radicals are weaker as supported both by magnetic data and DFT calculations. The nature of orbital overlap between the SOMOs of Fe(III) and π* orbital of the porphyrin was found to rationalise the observed exchange coupling, establishing such a complex magnetic exchange in this tetranuclear model with a significant bioinorganic relevance.

Alkoxy-Bridged Dicopper(II) Cores Meet Tetracyanonickelate Linkers: Structural, Magnetic, and Theoretical Investigation of Cu/Ni Coordination Polymers.

Two heterometallic Cu(II)/Ni(II) coordination polymers, [Cu2(Hbdea)2Ni(CN)4]n (1) and [Cu2(dmea)2Ni(CN)4]n·nH2O (2), were successfully self-assembled in water by reacting Cu(II) nitrate with H2bdea (N-butyldiethanolamine) and Hdmea (N,N-dimethylethanolamine) in the presence of sodium hydroxide and [Ni(CN)4]2-. These new coordination polymers were investigated by single-crystal and powder X-ray diffraction and fully characterized by FT-IR spectroscopy, thermogravimetry, elemental analysis, variable-temperature magnetic susceptibility measurements, and theoretical DFT and CASSCF calculations. Despite differences in crystal systems, in both compounds, each dinuclear building block [Cu2(μ-aminopolyalcoholate)2]2+ is bridged by diamagnetic [Ni(CN)4]2- linkers, resulting in 1D (1) or 2D (2) metal-organic architectures. Experimental magnetic studies show that both compounds display strong antiferromagnetic coupling (J = -602.1 cm-1 for 1 and -151 cm-1 for 2) between Cu(II) ions within the dimers mediated by the μ-O-alkoxo bridges. These results are corroborated by the broken symmetry DFT studies, which also provide further insight into the electronic structures of copper dimeric units. By reporting a facile self-assembly synthetic protocol, this study can be a model to widen a still limited family of heterometallic Cu/Ni coordination polymer materials with different functional properties.

Investigation of possible spin frustration in isolated isosceles MnIIINiII2 Triangle: Experimental and theoretical studies

Spin frustration is a unique phenomenon in magnetic complexes, where if a spin fails to lower the total energy of the system, by orienting itself in relative to its adjacent spins, it is termed as frustrated. In this work, we discuss about the magnetic properties, and the possibility of spin frustration in our isolated [NiII2MnIII(hep)4(PhCO2)(N3)2] (Hhep = 2-(2-hydroxyethyl) pyridine) having an isosceles NiII2MnIII triangle. The triangular MnIIINiII2 core was held together by two μ3-alkoxide bridges. The magnetic properties of this complex were studied in detail. Variable temperature magnetic susceptibility data of the complex in the range of 1.8 to 300 K, indicates the presence of stronger intramolecular antiferromagnetic coupling between two NiII centres than between NiII and MnIII ions. Experimentally, the ground state of the complex was found to be a mixture of E(2,0) and E(1,1) states, suggesting our complex to be close to a spin frustrated system which was supported by ab initio calculations.

Room-Temperature Entanglement of the Nickel-Radical Molecular Complex (Et3NH)[Ni(hfac)2L] Reinforced by the Magnetic Field

Bipartite entanglement is comprehensively investigated in the mononuclear molecular complex (Et3NH)[Ni(hfac)2L], where HL denotes 2-(2-hydroxy-3-methoxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl and hfacH stands for hexafluoroacetylacetone. From the magnetic point of view, the molecular compound (Et3NH)[Ni(hfac)2L] consists of an exchange-coupled spin-1 Ni2+ magnetic ion and a spin-12 nitronyl-nitroxide radical substituted nitrophenol. The nickel-radical molecular complex affords an experimental realization of a mixed spin-(12, 1) Heisenberg dimer with a strong antiferromagnetic exchange coupling, J/kB = 505 K, and two distinct g-factors, gRad = 2.005 and gNi = 2.275. By adopting this set of magnetic parameters, we demonstrate that the Zeeman splitting of a quantum ferrimagnetic ground-state doublet due to a weak magnetic field may substantially reinforce the strength of bipartite entanglement at low temperatures. The molecular compound (Et3NH)[Ni(hfac)2L] maintains sufficiently strong thermal entanglement, even at room temperature, vanishing only above 546 K. Specifically, the thermal entanglement in the nickel-radical molecular complex retains approximately 40% of the maximum value, corresponding to perfectly entangled Bell states at room temperature, which implies that this magnetic compound provides a suitable platform of a molecular qubit with potential implications for room-temperature quantum computation and quantum information processing.

Magnetic anisotropy, magnetization reversal and switching in Ni4Nb2O9 single crystals

Ni4Nb2O9 is an insulating compensated ferrimagnet with TN = 77 K and T comp= 33 K. We report here the study of the magnetic anisotropy using millimeter-size crystals grown in an image furnace. The magnetization measurements, vs temperature, performed with H aligned along the three main crystallographic axes, show similar Curie–Weiss temperatures (Θp ≈ 190 K) and rather similar effective paramagnetic moments (from 3.5 μ B to 3.6 μ B). This suggests that the strongest magnetic interaction is the antiferromagnetic one, coupling the ferromagnetic distorted honeycomb layers and zigzag ribbons via face sharing NiO6 octahedra. This strong antiferromagnetic coupling is supported by DFT calculations that do not evidence any inter site ferromagnetic interaction, leading to total compensation between magnetic moments of both Ni2+ sites. Measurements vs magnetic field below TN reveal an anisotropic behaviour, with square magnetization loops for H in the ab plane, whereas linear M(H) curves without hysteresis are observed for H‖c. This anisotropy between ab plane and c axis occurs also in the magnetization reversal (MR), which is observed in the ab plane only. Starting from M(H) virgin curves collected just below T comp= 33 K with H‖a or H‖b, the memory-like effect was tested through magnetization switching induced by H or T alternating changes. Below T comp, smaller H is needed to switch M symmetrically for H along b than along a, and, for T switching (2 K interval, constant H), a larger M change is obtained along a than along b. The comparison with ferrimagnetic oxides which exhibit MR, like spinels or rare earth orthoferrites, shows that Ni4Nb2O9 is unique since only one magnetic cation over two sites in octahedral coordination is at play, thus providing a unique platform to study M switching but also a challenge for theoretical interpretation.

Er-driven incommensurate to commensurate magnetic phase transition of Fe in the spin-chain compound BaErFeO4

Magnetic phase transitions and structures of the spin-chain compound BaErFeO4 were investigated by measurements of magnetic properties (specific heat, magnetic susceptibility) and neutron diffraction. The lattice geometry of the orthorhombic crystal structure (space group ) of the BaRFeO4 compounds (R=Dy–Yb, Y) supports frustrations which lead to multiple magnetic phase transitions with complex magnetic structures. BaErFeO4 undergoes three successive magnetic phase transitions at TN1=49K, TN2=33.4K, and TN3=3.4K. In contrast with the previously investigated BaRFeO4 (R=Y, Tm, Yb) compounds, all with incommensurate magnetic propagation vectors k1=(0,0,kz), BaErFeO4 is the first member in this series that shows a phase transition from an incommensurate (k1 below TN1) to a commensurate magnetic structure with k2=(12,0,12) below TN2. In the crystal structure, all magnetic ions (Fe1, Fe2, Er1, and Er2) are part of chains propagating along the b axis. Below TN1, strong antiferromagnetic (AFM) Fe-Fe spin-exchange coupling between square pyramidal (Fe1) and octahedral (Fe2) centers generates a collinear AFM structure with a constant size of the ordered Fe moments and a constant magnetic phase inside each chain of Fe3+ cations. Exchange coupling between the Fe chains is much weaker. At TN2, 3d−4f exchange interactions induce an ordered moment at the Er3+ ions, which results in a change of the direction of the ordered Fe moments from the b direction (above TN2) to inside the ac plane (below TN2) and a change from an incommensurate (k1 above TN2) to a commensurate (k2 below TN2) AFM structure. Toward lower temperature, 4f−4f exchange interactions become stronger and create at TN3 a constant magnetic phase inside each chain of Er3+ cations. At TN2 and TN3, the magnetic susceptibility shows sharp decreases that coincide with large increases of the correlation length of the magnetic structure. The unique magnetic structures of BaErFeO4 are compared with those of other BaRFeO4 compounds by considering experimental and theoretical aspects. ©2024 American Physical Society 2024 American Physical Society

Antiaromatic Molecules as Magnetic Couplers: A Computational Quest.

In this study, we investigate a set of organic diradical structures in which two oxo-verdazyl radicals are selected as radical spin centers that are connected (coupled) via six coupler molecules (CM), resulting in various magnetic (ferromagnetic (FM) or antiferromagnetic (AFM)) characteristics, as reflected by their exchange coupling constants (J). We have designed 12 diradicals with 6-antiaromatic couplers coupled with bis-oxo-verdazyl diradicals with meta-meta (m-m) and para-meta (p-m) positional connectivities. The nature of the magnetic coupling (ferromagnetic, nonmagnetic, or antiferromagnetic) and the magnitude of the exchange constant J depend on the type of coupler, the connecting point between each radical center and CM, the degree of aromaticity of the coupler, and the length of the through-bond distance between radical centers. The computed magnetic exchange coupling constants J for these diradicals at the B3LYP/6-311++G(d,p) and MN12SX/6-311++G(d,p) levels of theory are large for many of these structures, indicating strong ferromagnetic coupling (with positive J values). In some cases, magnetic couplings are observed with J > 1000 cm-1 (B3LYP/6-311++G(d,p)) and strong antiferromagnetic coupling (with negative J values) with J < -1000 cm-1 (B3LYP/6-311++G(d,p)). Similarly, in some cases, magnetic couplings are observed with J > 289 cm-1 (MN12SX/6-311++G(d,p)) and strong antiferromagnetic coupling (with negative J values) with J < -568 cm-1 (MN12SX/6-311++G(d,p)). Furthermore, while numerous studies have reported that the degree of aromaticity of molecular couplers often favors strong ferromagnetic coupling, displaying the high-spin character of diradicals in their ground states, the couplers chosen in this study are characterized as antiaromatic or nonaromatic. The current investigation provides evidence that, remarkably, antiaromatic couplers are able to enhance stability by favoring electronic diradical structures with very strong ferromagnetic coupling when the length of the through-bond distance and connectivity pattern between radical centers are selected in such a way that the FM coupling is optimized. The findings in this study offer new strategies in the design of novel organic materials with interesting magnetic properties for practical applications.

Dinitrogen Activation Mediated by the (P2PPh)Fe Complex: Electronic Structure, Dimerization Mechanism, and Magnetic Coupling.

Herein, we report the estimation of the extent of dinitrogen activation by different charged and structural forms of (P2PPh)Fe biomimetic catalysts, which, in the presence of light, exhibit significant yield in the N2-to-NH3 conversion. Complete active space self-consistent field (CASSCF) calculations have been used to determine the electronic structure of different reduced forms of the mononuclear complexes: the neutral (P2PPh)Fe(N2)2 adduct and the anionic [(P2PPh)Fe(N2)]- and [(P2PPh)Fe(N2)]2- complexes. These calculations also revealed that the extent of reduction of a dinitrogen molecule reaches up to one electron (N21-) due to the back-bonding from the Fe center, in agreement with the changes observed in the vibration frequency of the N-N bond in these complexes. In addition, the energy profile of the dimerization of the mononuclear (P2PPh)Fe(N2)2 complex to the dinuclear mono-N2-bridged [(P2PPh)Fe]2(μ-N2) complex has been determined by means of density functional theory (DFT) calculations. A three-step mechanism has been proposed for the dimerization, favored by both kinetics and thermodynamics criteria. Finally, the magnetic coupling constant in the diiron (μ-N2) complex is estimated from CASSCF/NEVPT2 calculations. Such a dinuclear complex presents a strong antiferromagnetic coupling resulting from the interaction between two S = 1 d6 Fe2+ ions, bridged by a highly activated dinitrogen molecule (N22-) with two electrons on the π* orbitals.

Tuning the magnetic coupling between manganese porphyrins in the 2MnIITPP⋅L assemblies, where L is 6,13-pentacenequinone, isoviolanthrone2− and {MnII(triazole−)2Pc}2−. Key role of a linker (L) in magnetic exchange

Coordination architectures involving high-spin S = 5/2 manganese (II) tetraphenylporphyrins (MnIITPP) and a series of π-conjugated linkers have been obtained. Different molecules (isoviolanthrone, 6,13-pentacenequinone, 1,2,4-triazole anions coordinated to manganese (II) phthalocyanine [(MnII(triazole−)2Pc)]2−) in either dianion or neutral states were used as linkers in these architectures. Complexes [cryptand(K+)]2⋅[(isoviolanthrone2−)⋅{MnIITPP}2]2−⋅5C6H4Cl2 (1) and [(6,13-pentacenequinone0)⋅{MnIITPP}2]0⋅2C6H4Cl2 (2) are formed as a result of the reaction of MnIITPP with isoviolanthrone2− or MnIIIClTPP with 6,13-pentacenequinone2−. Rather weak magnetic coupling between MnII atoms is due to their large spatial separation by diamagnetic isoviolanthrone2− or pentacenequinone0 linkers. Two MnIITPP units are bridged by a paramagnetic [(MnII(triazole−)2Pc)]2− dianion linker with low-spin S = 1/2 manganese(II) atoms within Pc in [cryptand(Na+)]2⋅[(MnII(triazole−)2Pc)⋅{MnIITPP}2]2−⋅5C6H4Cl2 (3). As a result, a triple-decker homotrimetallic [(MnII(triazole−)2Pc)⋅{MnIITPP}2]2− anionic assembly is formed with three paramagnetic nuclei having S = 1/2 and 5/2 spin states, respectively. Strong antiferromagnetic coupling between high-spin outer MnIITPP and low-spin central MnIIPc units is observed in 3 with J = - 35.2 cm−1. Such coupling induces a parallel alignment of outer S = 5/2 spins antiparallel to the central S = 1/2 spin yielding the high-spin S = 9/2 state at 2 K. X-ray crystallography, spectral, magnetic susceptibility data, and EPR are in line with these assignments.