Enhancing Intramolecular Ferromagnetic Coupling in Tetrathiafulvalene-Nitronyl Nitroxide-Based Compounds through Spin Polarization Mechanism.

Spin-polarized donor radicals based on tetrathiafulvalene (TTF) derivatives and nitronyl nitroxide (NN) radicals in which one-electron oxidation involves the HOMO instead of the SOMO are well known for exhibiting magnetoresistance. In particular, BTBN consists of one dibromo-TTF and one NN radical, which are linked by a phenyl coupler group. One of the key factors driving magnetoresistance is the presence of intramolecular ferromagnetic (FM) coupling between the oxidized π-donor (TTF+⋅, D unit) and NN (R unit). Here, a theoretical study is carried out to assess suitable candidates with enhanced FM coupling with respect BTBN, which is thus used as a reference. The study is conducted via in silico chemical modification of the substituents of the BTBN basic functional units (D and R radicals, C coupler) to benefit from the spin polarization mechanism to boost the intramolecular FM coupling, aiming to distort the BTBN radical arrangement within the molecular crystal as little as possible, in the event the material can be synthesized. NICSiso(1) and Wiberg's Bond Order are analyzed to further assist in identifying promising potential candidates, since the decrease in aromaticity is expected to enhance the diradical character and give rise to a larger magnetic coupling value. The most favorable diradical building block to replace the BTBN moiety results from using a hydroxyl-ethylene (-(H)C=C(OH)-) as a coupler preserving BTBN original radicals, namely, NN and TTF+⋅ units. This study aims at illustrating the feasibility of improving the intramolecular FM interaction between radical moieties, which is fully realized, as a first step towards the synthesis of new materials with (possibly) enhanced magnetoresistance properties.

Satellite ligand effects on magnetic exchange in dimers. A structural, magnetic and theoretical investigation of Cu2L2X4 (L = methylisothiazolinone and X = Cl-, Br-).

Halide-bridged polymers have gained significant interest due to their diverse properties and potential applications. Stacked Cu2L2X4 dimers, where L is an organic ligand and X can be Cl- or Br-, are of interest because a chloride analogue where L = 2-pyridone, had previously been reported to exhibit bulk ferromagnetism, which augured great potentiality for this class of compounds. The synthesis, structural characterization, magnetic susceptibility measurements, and computational studies of two isostructural CuClMI (MI = methylisothiazolinone) and CuBrMI polymers of Cu(II), along with a related CuClPYR (PYR = 2-pyridone) is reported. CuClMI and CuBrMI were found to exhibit AFM bulk properties, due to FM/AFM alternating chains along the halide-bridged polymer axis, while FM bulk properties were confirmed for CuClPYR exhibiting a FM spin ladder. In combination with a benzamide analogue, CuClBA, three O-donor amides, CuClMI, CuClBA and CuClPYR were analyzed and revealed that the kinetic exchange is affected by the identity, but more importantly, the orientation of the satellite ligands. The torsional angle of the ligand with the dimer plane is shown to significantly affect the magnetic exchange in the dimer, and between dimers, explaining the reported FM bulk properties of CuClPYR. This finding is exceedingly important, as it suggests that a spin device can be constructed to flip between singlet/triplet states by manipulating the orientation of the satellite/terminal ligand.

Electronic structure and magnetic coupling in selenium substituted pyridine-bridged bisdithiazolyl multifunctional molecular materials.

Bisdithiazolyl radicals have furnished in recent years multiple examples of molecular materials with promising conductive and magnetic properties. The electronic band structure and magnetic ordering in four different isostructural pyridine-bridged bisdithiazolyl and Selenium substituted compounds have been studied by means of hybrid DFT based methods as implemented in the CRYSTAL code. The full rationalization of the properties of these multifunctional magnetic molecular materials requires a careful description of their complex open-shell electronic structure. The results describe the systems as narrow band (0.2-0.3 eV dispersion) open-shell semiconductors with a gap of 1.15-1.40 eV between the valence and conducting bands. The bands defining the insulating gap are dominated by orbital contributions arising from the heteroatoms sitting in the outer rings. A low energy closed-shell metallic solution is found at 0.25-0.35 eV above the magnetic solutions thus suggesting a complex mechanism for electric conduction with band and hopping contributions. The observed trend of the conductivity is in line with the variation of the insulating gap but more rigorous modelling is required to take into account the details of the band structure of the systems. For all the systems the spin density is well localised on the molecular units and is independent of the magnetic solution. Thus the system can be described as an ensemble of well-defined S = 1/2 magnetic centres using a two-body Heisenberg-Dirac-van Vleck spin Hamiltonian. The lowest energy electronic solutions are in line with the observed magnetic behaviour at low temperature. The set of competing magnetic exchange interactions that emerges from using a suitable mapping to consistently describe the low energy magnetic solutions explains the variety of magnetic responses (absence of long-range magnetic order, antiferromagnetism or ferromagnetism) of the four studied compounds at low temperatures.

Approaching the isotropic spin-ladder regime: structure and magnetism of all-pyrazine-bridged copper(II)-based antiferromagnetic ladders.

The crystal structure and magnetic properties of two all-pyrazine-bridged antiferromagnetic spin ladders are reported. The complexes, catena-(bis(3-X-4-pyridone)(µ-pyrazine)copper(II)(-µ-pyrazine)diperchlorate ([Cu(pz)1.5(L)2](ClO4)2 where L = 3-X-4-pyridone and X = Br (1) or Cl (2)), contain copper(II)-based ladders in which both the rung and rail bridges are pyrazine molecules bonded through the x2-y2 orbital of the copper(II) ions. This structural scaffold is proposed to approach the isotropic spin-ladder regime. 1 and 2 crystallize in the monoclinic space group P21/c. Due to the bulk of the 3-X-4-HOpy ligands, the ladders are well isolated in the a-direction (1, 15.6 Å; 2, 15.5 Å). The ladders, which run in the b-direction, are stacked in the c-direction with the separation (1, 7.87 Å; 2, 7.82 Å) between copper(II) ions caused by the bulk of a semi-coordinate perchlorate ion coordinated in the axial position. Computational evaluation of magnetic JAB couplings between Cu-moieties of 2 supports the experimentally proposed magnetic topology and agrees with an isolated isotropic spin-ladder (Jrail = -4.04 cm-1 (-5.77 K) and Jrung = -3.89 cm-1 (-5.56 K)). These complexes introduce a convenient scaffold for synthesizing isotropic spin-ladders with modest superexchange interactions, the strength of which may be tuned by variations in L. The magnetic susceptibility down to 1.8 K, for both compounds, is well described by the strong-rung ladder model giving nearly isotropic exchange with Jrung ≈ Jrail ≈ -5.5 K (1) and -5.9 K (2) using the Hamiltonian. Theoretical simulations of the magnetic response of 2 using the isotropic ladder model are in excellent agreement with experiment. The measured magnetization to 5 T indicates a quantum-dominated magnetic spectrum. Again, calculated lower and saturation (4.3 and 24 T, respectively) critical fields for 2 are consistent with experimental measurements, and magnetization data at very low temperatures indeed suggest the presence of quantum effects. Further, the computational study of short- and long-range spin ordering indicates that a 2D-to-3D crossover might be feasible at lower temperatures. Analysis of the Boltzmann population corroborates the presence of accessible triplet states above the singlet ground state enabling the aforementioned 2D-to-3D crossover.

Controlling pairing of π-conjugated electrons in 2D covalent organic radical frameworks via in-plane strain.

Controlling the electronic states of molecules is a fundamental challenge for future sub-nanoscale device technologies. π-conjugated bi-radicals are very attractive systems in this respect as they possess two energetically close, but optically and magnetically distinct, electronic states: the open-shell antiferromagnetic/paramagnetic and the closed-shell quinoidal diamagnetic states. While it has been shown that it is possible to statically induce one electronic ground state or the other by chemical design, the external dynamical control of these states in a rapid and reproducible manner still awaits experimental realization. Here, via quantum chemical calculations, we demonstrate that in-plane uniaxial strain of 2D covalently linked arrays of radical units leads to smooth and reversible conformational changes at the molecular scale that, in turn, induce robust transitions between the two kinds of electronic distributions. Our results pave a general route towards the external control, and thus technological exploitation, of molecular-scale electronic states in organic 2D materials.

Revisiting the Role of Hydrogen Bonding in the Strong Dimer Superexchange of a 2D Copper(II) Halide Honeycomb-Like Lattice: Structural and Magnetic Study.

The title compound H2L(CuCl3H2O)Cl (H2L = 1-(4'-pyridinium)pyridin-4-ol-ium), 1) was synthesized and investigated structurally and magnetically as well as via a first-principles, bottom-up theoretical analysis of the potential magnetic superexchange pathways. Compound 1 can be described structurally as a well-isolated, distorted 2D-honeycomb lattice with two potential exchange pathways: a dimeric interaction via hydrogen-bonded pairs of (CuCl3H2O) ions and a chain structure via bridging chloride ions. Surprisingly, the experimental magnetic data are best fitted using both a simple dimer model with a Curie-Weiss correction for interdimer exchange (Jdimer = -107.4(1) K, θ = -1.22(4) K) and a strong-rung ladder model (Jrung = -105.8(7) K, Jrail = 2(7) K). Theoretical analysis at the UB3LYP/6-31+G(d) level supports the strong exchange observed through the [CuCl4(H2O)]2- dimer moiety superexchange pathway (-102 K = -71 cm-1). However, the apparent vanishingly small exchange through the single halide bridge is merely a brute average of competing ferromagnetic (FM) (+24.8 K = +17.0 cm-1) and antiferromagnetic (AFM) (-21.0 K = -14.6 cm-1) exchange interactions. Our computational study shows that these fitting parameters carry no physical meaning since a honeycomb plaquette must be taken as magnetic building block for 1. The competition between FM and AFM pair interactions leads to geometrical frustration in 1 and could induce interesting magnetic response at low temperatures, if the magnetic exchange is adequately tuned by modifying substituents in ligands and, in turn, interactions within the crystal packing.

Revising the common understanding of metamagnetism in the molecule-based bisdithiazolyl BDTMe compound.

The BDTMe molecule-based material is the first example of a thiazyl radical to exhibit metamagnetic behavior. Contrary to the common idea that metamagnetism occurs in low-dimensional systems, it is found that BDTMe magnetic topology consists of a complex 3D network of almost isotropic ferromagnetic spin-ladders that are coupled ferromagnetically and further connected by some weaker antiferromagnetic interactions. Calculated magnetic susceptibility χT(T) data is in agreement with experiment. Calculated M(H) data clearly show the typical sigmoidal shape of a metamagnet at temperatures below 2 K. The calculated critical field becomes more apparent in the dM/dH(H) plot, being in very good agreement with experiment. Our computational study concludes that the magnetic topology of BDTMe is preserved throughout the entire experimental range of temperatures (0-100 K). Accordingly, the ground state is the same irrespective of the temperature at which we study the BDTMe crystal. Revising the commonly accepted understanding of a metamagnet explained as ground state changing from antiferromagnetic to ferromagnetic, the Boltzmann population of the different states is here suggested to be the key concept: at 2 K the ground singlet state has more weight (24%) than at 10 K (1.5%), where excited states have an important role. Changes in the antiferromagnetic interactions that couple the ferromagnetic skeleton of BDTMe will directly affect the population of the distinct states that belong to a given magnetic topology and thus its magnetic response. Accordingly, this strategy could be valid for a wide range of bisdithiazolyl BDT-compounds whose magnetism can be tuned by means of weak antiferromagnetic interactions.

The magnetic fingerprint of dithiazolyl-based molecule magnets.

Magnetic bistability in organic-radical based materials has attracted significant interest due to its potential application in electronic devices. The first-principles bottom-up study herein presented aims at elucidating the key factors behind the different magnetic response of the low and high temperature phases of four different switchable dithiazolyl (DTA)-based compounds. The drastic change in the magnetic response upon spin transition is always due to the changes in the JAB magnetic interactions between adjacent radicals along the π-stacks of the crystal, which in turn are driven mostly by the changes in the interplanar distance and degree of lateral slippage, according to the interpretation of a series of magneto-structural correlation maps. Furthermore, specific geometrical dispositions have been recognized as a ferromagnetic fingerprint in such correlations. Our results thus show that an appropriate substitution of the chemical skeleton attached to the DTA ring could give rise to new organic materials with dominant ferromagnetic interactions.

A Definition of the Magnetic Transition Temperature Using Valence Bond Theory.

Macroscopic magnetic properties are analyzed using Valence Bond theory. Commonly the critical temperature TC for magnetic systems is associated with a maximum in the energy-based heat capacity Cp(T). Here a more broadly applicable definition of the magnetic transition temperature TC is described using the spin moment expectation value (i.e., applying the spin exchange density operator) instead of energy. Namely, the magnetic capacity Cs(T) reflects variation in the spin multiplicity as a function of temperature, which is shown to be related to ∂[χT(T)]/∂T. Magnetic capacity Cs(T) depends on long-range spin interactions that are not relevant in the energy-based heat capacity Cp(T). Differences between Cs(T) and Cp(T) are shown to be due to spin order/disorder within the crystal that can be monitored via a Valence Bond analysis of the corresponding magnetic wave function. Indeed the concept of the Boltzmann spin-alignment order is used to provide information about the spin correlation between magnetic units. As a final illustration, the critical temperature is derived from the magnetic capacity for several molecular magnets presenting different magnetic topologies that have been experimentally studied. A systematic shift between the transition temperatures associated with Cs(T) and Cp(T) is observed. It is demonstrated that this shift can be attributed to the loss of long-range spin correlation. This suggests that the magnetic capacity Cs(T) can be used as a predictive tool for the magnetic topology and thus for the synthetic chemists.

The quest for rationalizing the magnetism in purely organic semiquinone-bridged bisdithiazolyl molecular magnets.

Semiquinone-bridged bisdithiazolyl-based radicals (XBBO) are appealing purely organic magnetic building blocks for the synthesis of new functional materials. Remarkably, for the phenyl-derivative PhBBO, the rationalization of its magnetism becomes a proof of concept that DFT can dramatically fail to evaluate JAB magnetic interactions between purely organic radical pairs. Instead, wavefunction-based methods are required. Once JAB's are fully characterized, the magnetic topology of PhBBO is disclosed to consist of ferromagnetic FM π-stacks that are very weakly coupled (by FM and AFM JAB interactions). The magnetic susceptibility χT(T) and magnetization M(H) of PhBBO are then calculated using a first-principles bottom-up approach. The study of the unit cell contraction upon cooling from room temperature to zero-Kelvin is relevant to propose a suitable model for the phase transition that occurs at 4.5 K. A simplistic picture tells us that the antiparallel-aligned 1D-FM-chains convert into domains of weakly either FM- or AFM-coupled 1D-FM-chains. Accordingly, the presence of these domains may introduce geometrical spin frustration below 4.5 K.

The origin of the antiferromagnetic behaviour of the charge-transfer compound (HMTTF)[Ni(mnt)2].

The charge-transfer (HMTTF)[Ni(mnt)2] material (1) was the first mixed-stack compound reported to present ferromagnetic (FM) interactions between the donor (D) and acceptor (A) units within each mixed-stack. Despite the presence of a dominant FM interaction, its magnetic susceptibility curve, χ(T), corresponded to that of an antiferromagnetic (AFM) compound at low temperatures, a fact that was tentatively explained in terms of a FM-to-AFM magnetic transition. In this work, the First-Principles Bottom-Up procedure has been applied to rationalize the magnetic properties of 1. The results presented herein indicate the presence of up to five sizeable JAB magnetic exchange interactions (26.0, -1.7, 1.9, 0.1, and -99.3 cm(-1)) that create a complex 2D magnetic network. This magnetic topology not only produces a calculated χ(T) curve that is in excellent agreement with the experimental measurements, but also allows us to understand the magnetic behaviour of 1, in the full range of temperatures, solely in terms of the different Boltzmann population of diamagnetic and paramagnetic spin states as the temperature changes. Our data thus provide a plausible explanation for the AFM behaviour of 1 at low temperatures that does not involve a phase transition.

Dynamical effects on the magnetic properties of dithiazolyl bistable materials.

The magnetic properties of molecule-based magnets are commonly rationalized by considering only a single nuclear configuration of the system under study (usually an X-ray crystal structure). Here, by means of a computational study, we compare the results obtained using such a static approach with those obtained by explicitly accounting for thermal fluctuations, and uncover the serious limitations of the static perspective when dealing with magnetic crystals whose radicals undergo wide-amplitude motions. As a proof of concept, these limitations are illustrated for the magnetically bistable 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) material. For its high-temperature phase at 300 K, we show that nuclear dynamics induce large fluctuations in the magnetic exchange interactions (JAB) between spins (up to 1000% of the average value). These deviations result in a ∼20% difference between the 300 K magnetic susceptibility computed by explicitly considering the nuclear dynamics and that computed using the X-ray structure, the former being in better agreement with the experimental data. The unveiled strong coupling between JAB interactions and intermolecular vibrations reveals that considering JAB as a constant value at a given temperature (as always done in molecular magnetism) leads to a flawed description of the magnetism of TTTA. Instead, the physically relevant concept in this case is the statistical distribution of JAB values. The discovery that a single X-ray structure is not adequate enough to interpret the magnetic properties of TTTA is also expected to be decisive in other organic magnets with dominant exchange interactions propagating through labile π-π networks.

The key role of vibrational entropy in the phase transitions of dithiazolyl-based bistable magnetic materials.

The neutral radical 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) is a prototype of molecule-based bistable materials. TTTA crystals undergo a first-order phase transition between their low-temperature diamagnetic and high-temperature paramagnetic phases, with a large hysteresis loop that encompasses room temperature. Here, based on ab initio molecular dynamics simulations and new X-ray measurements, we uncover that the regular stacking motif of the high-temperature polymorph is the result of a fast intra-stack pair-exchange dynamics, whereby TTTA radicals continually exchange the adjacent TTTA neighbour (upper or lower) with which they form an eclipsed dimer. Such unique dynamics, observed in the paramagnetic phase within the whole hysteresis loop, is the origin of a significant vibrational entropic gain in the low-temperature to high-temperature transition and thereby it plays a key role in driving the phase transition. This finding provides a new key concept that needs to be explored for the rational design of novel molecule-based bistable magnetic materials.

S=1/2 one-dimensional random-exchange ferromagnetic zigzag ladder, which exhibits competing interactions in a critical regime.

The synthesis, crystal structure, and magnetic properties (from a combined experimental and First-Principles Bottom-Up theoretical study) of the new compound catena-dichloro(2-Cl-3Mpy)copper(II), 1, [2-Cl-3Mpy=2-chloro-3-methylpyridine] are described and rationalized. Crystals of 1 present well isolated magnetic 1D chains (no 3D order was experimentally observed down to 1.8 K) and magnetic frustration stemming from competing ferromagnetic nearest-neighbor (J(NN)) interactions and antiferromagnetic next-nearest neighbor (J(NNN)) interactions, in which α=J(NNN)/J(NN) <-0.25. These magnetic interactions give rise to a unique magnetic topology: a two-leg zigzag ladder composed of edge-sharing up-down triangles with antiferromagnetic interactions along the rails and ferromagnetic interactions along the zigzag chain that connects the rails. Crystals of 1 also present a random distribution of the 2-Cl-3Mpy groups, which are arranged in two different orientations, each with a 50 % occupancy. This translates into a random static structural disorder within each chain by virtue of which the value of the J(NN) magnetic interactions can randomly take one of the following three values: 53, 36, and 16 cm(-1). The structural disorder does not affect the J(NNN) value, which in all cases is approximately -9 cm(-1). A proper statistical treatment of this disorder provides a computed magnetic susceptibility curve that reproduces the main features of the experimental data.

Elucidating the 2D magnetic topology of the 'metal-radical' TTTA⋠Cu(hfac)2 system.

The TTTA⋅Cu(hfac)2 polymer (1; in which TTTA = 1,3,5-trithia-2,4,6-triazapentalenyl, and hfac = (1,1,1,5,5,5)-hexafluoroacetylacetonate) is one of the most prominent examples of the rational use of the 'metal-radical' synthetic approach to achieve ferromagnetic interactions. Experimentally, the magnetic topology of 1 could not be fully deciphered. Herein, the first-principles bottom-up procedure was applied to elucidate the nature and strength of the magnetic JAB exchange interactions present in 1. The computed JAB values give rise to a 2D magnetic topology of ferromagnetic dimers (+11.9 cm(-1)) coupled through weaker antiferromagnetic interactions (-3.0 and -3.2 cm(-1)) in two different spatial directions. The hitherto unknown origin of the antiferromagnetic interdimer interactions is thus unveiled. By using the 2D magnetic topology, the agreement between calculated and experimental χT(T) data is extraordinary. In the metal-radical TTTA⋅Cu(hfac)2 compound, the computational model transcends the local dimer cluster model owing to strong interactions between metal centers and organic radicals, thereby creating a de facto biradical. In addition, it is shown that the magnetic topology cannot be inferred from the polymeric [TTTA⋅⋅⋅Cu(hfac)2]n crystal motif, that is, from its chemical coordination pattern. Instead, one should think in terms of magnetic building blocks, namely, the de facto biradicals.

Dividing the spoils: role of pyrazine ligands and perchlorate counterions in the magnetic properties of bis(pyrazine)diperchloratecopper(II), [Cu(pz)2](ClO4)2.

A complete first-principles bottom-up computational study of the magnetic properties of [Cu(pz)2](ClO4)2 is presented. A remarkable agreement is observed in the whole range of temperatures between simulated and experimental magnetic susceptibility data. Interestingly, the simulated heat capacity values show an anomaly close to the Néel temperature of 4.21 K associated with a transition from a two-dimensional (2D) antiferromagnet to a three-dimensional (3D) ordered state. The antiferromagnetic behavior of [Cu(pz)2](ClO4)2 is due to a 2D magnetic topology owing to two antiferromagnetic J(AB) interactions through pyrazine ligands. Although presenting a very similar molecular arrangement, the numerical values of the two magnetically significant J(AB) couplings differ by 25% (-10.2 vs -7.3 cm(-1)). This difference can be ascribed to three main contributions: (i) the central pyrazine ring shearing-like distortion, (ii) the effect of the orientation of the perchlorate counterions, and (iii) a hitherto unrecognized skeleton-counterion cooperation arising from different hydrogen bonding contributions in the two most significant J(AB) couplings. The impact of the orientation of the perchlorate counterions is disclosed by comparison to J(AB) studies using structurally similar ligands but with different electronegativity (namely, BF4(-), BCl4(-), and BBr4(-)). Pyrazine ligands and perchlorate counterions prove to be noninnocent.

Tracing the sources of the different magnetic behavior in the two phases of the bistable (BDTA)2[Co(mnt)2] compound.

A complete computational study of the magnetic properties of the two known phases of the bistable (BDTA)(2)[Co(mnt)(2)] compound is presented. The origin of their different magnetic properties can be traced to a variation in the values of the g tensor, together with a hitherto unknown change in the J(AB) values and their magnetic topology.

Synthesis, structure, magnetic behavior, and theoretical analysis of diazine-bridged magnetic ladders: Cu(quinoxoline)X2 and Cu(2,3-dimethylpyrazine)X2 (X = Cl, Br).

The synthesis, structure, and magnetic behavior of the complexes Cu(qnx)Br(2) (1), Cu(2,3-dmpz)Br(2) (2), Cu(qnx)Cl(2) (3), and Cu(2,3-dmpz)Cl(2) (4) (qnx = quinoxaline, dmpz = dimethylpyrazine) are described. Both X-ray structural data and fitting of the magnetic data suggest that the compounds are well-described as strong-rung, two-leg magnetic ladders with J(rung) ranging from -30 K to -37 K, and J(rail) ranging from -14 K to -24 K. An unexpected decrease in the exchange constant for J(rail) (through the diazine ligand) is observed when the halide ion is changed from bromide to chloride, along with a small decrease in the magnetic exchange through the halide ion. Theoretical calculations on 2 and 4 via a first-principles bottom-up approach confirmed the description of the complexes as two-leg magnetic ladders. Furthermore, the calculations provide an explanation for the experimentally observed change in the value of the magnetic exchange through the dmpz ligand when the halide ion is changed from bromide to chloride, and for the very small change observed in the exchange through the different halide ions themselves via a combination of changes in geometry, bond lengths, and anion volume.

Origin of the magnetic bistability in molecule-based magnets: a first-principles bottom-up study of the TTTA crystal.

The magnetic bistability present in some molecule-based magnets is investigated theoretically at the microscopic level using the purely organic system TTTA (1,3,5-trithia-2,4,6-triazapentalenyl). The TTTA crystal is selected for being one of the best-studied molecule-based systems presenting magnetic bistability. The magnetic properties of the high- and low-temperature structures (HT and LT phases, respectively) are accurately characterized by performing a First-Principles Bottom-Up study of each phase. The changes that the magnetic exchange coupling constants (J(AB)) undergo when the temperature is raised (LT → HT) or lowered (HT → LT) are also fully explored in order to unravel the reasons behind the presence of these two different pathways. The triclinic LT phase is diamagnetic due to the fact that the nearly eclipsed π dimer is effectively magnetically silent and not to formation of a covalent bond between two TTTA molecules. It is also shown that bistability in TTTA results from the coexistence of the monoclinic HT and triclinic LT phases in the temperature range studied.

The magnetism of (5MAP)2CuBr4 [5MAP = 5-methyl-2-aminopyridinium]: a quasi-2D or a 3D magnetic system?

In order to determine if its magnetic topology is actually two- or three-dimensional (2D or 3D), the mechanism of the magnetic interaction in (5MAP)(2)CuBr(4), a previously thought quasi-2D antiferromagnet, is re-examined using the first-principles bottom-up methodology. Once the magnitude and sign of all unique magnetic interactions present in the room-temperature (5MAP)(2)CuBr(4) crystal are evaluated, it is found that, even at room temperature, the magnetic topology of the crystal corresponds to a 3D antiferromagnet. Such 3D nature cannot be determined by examination of the magnetic susceptibility curve, chi(T), because it is found that the chi(T) curve computed using this 3D magnetic topology is very similar to that obtained using a 2D model where all interplane interactions have been deleted. However, its 3D magnetic dimensionality can be confirmed by examination of the shape of the magnetization curve, M(H); the computed curve is similar to the experimental one for the 3D case.