Daniel Reta Mañeru

The Triplet–Singlet Gap in the m-Xylylene Radical: A Not So Simple One

Meta-benzoquinodimethane (MBQDM) or m-xylylene provides a model for larger organic diradicals, the triplet-singlet gap being the key property. In the present work this energy difference has been the object of a systematic study by means of several density functional theory-based methods including B3LYP, M06, M06-2X, HSE and LC-ωPBE potentials and a variety of wave function-based methods such as complete active space self consistent field (CASSCF), Multireference second-order Møller-Plesset (MRMP), difference dedicated configuration interaction (DDCI), and Multireference configuration interaction (MRCI). In each case various basis sets of increasing quality have been explored, and the effect of the molecular geometry is also analyzed. The use of the triplet and broken symmetry (BS) solutions for the corresponding optimized geometries obtained from B3LYP and especially M06-2X functionals provide the value of the adiabatic triplet-singlet gap closer to experiment when compared to the reported value of Wenthold, Kim, and Lineberger, (J. Am. Chem. Soc. 1997, 119, 1354) and also for the electron affinity. The agreement further improves using the full π-valence CASSCF(8,8) optimized geometry as an attempt to correct for the spin contamination effects on the geometry of the BS state. The CASSCF, MRMP, and MRCI, even with the full π valence CAS(8,8) as reference and relatively large basis set, systematically overestimate the experimental value indicating either that an accurate description must go beyond this level of theory, including σ electrons and higher order polarization functions, or perhaps that the measured value is affected by the experimental conditions.

Discovery of the K4 Structure Formed by a Triangular π Radical Anion.

The K4 structure was theoretically predicted for trivalent chemical species, such as sp(2) carbon. However, since attempts to synthesize the K4 carbon have not succeeded, this allotrope has been regarded as a crystal form that might not exist in nature. In the present work, we carried out electrochemical crystallization of the radical anion salts of a triangular molecule, naphthalene diimide (NDI)-Δ, using various electrolytes. X-ray crystal analysis of the obtained crystals revealed the K4 structure, which was formed by the unique intermolecular π overlap directed toward three directions from the triangular-shape NDI-Δ radical anions. Electron paramagnetic resonance and static magnetic measurements confirmed the radical anion state of NDI-Δ and indicated an antiferromagnetic intermolecular interaction with the Weiss constant of θ = -10 K. The band structure calculation suggested characteristic features of the present material, such as a metallic ground state, Dirac cones, and flat bands.

Spin adapted versus broken symmetry approaches in the description of magnetic coupling in heterodinuclear complexes

The performance of a series of wave function and density functional theory based methods in predicting the magnetic coupling constant of a family of heterodinuclear magnetic complexes has been studied. For the former, the accuracy is similar to other simple cases involving homodinuclear complexes, the main limitation being a sufficient inclusion of dynamical correlation effects. Nevertheless, these series of calculations provide an appropriate benchmark for density functional theory based methods. Here, the usual broken symmetry approach provides a convenient framework to predict the magnetic coupling constants but requires deriving the appropriate mapping. At variance with simple dinuclear complexes, spin projection based techniques cannot recover the corresponding (approximate) spin adapted solution. Present results also show that current implementation of spin flip techniques leads to unphysical results.

Handling Magnetic Coupling in Trinuclear Cu(II) Complexes.

The problem of deriving three different two-body magnetic couplings in three electrons/three centers in a general geometric arrangement is investigated using the trinuclear Cu(II) HAKKEJ complex as a real case example. In these systems, one quartet and two doublet low lying electronic states exist, which define the magnetic spectra. However, the two possible linearly independent energy differences do not provide enough information to extract the three magnetic coupling constants. Here, we show how to obtain these parameters without making any assumption on the symmetry of the system from a combination of density functional- and wave function-based calculations. The density functional calculations explore various broken symmetry solutions and relate the corresponding energy to the expectation value of the Heisenberg Hamiltonian. This allows one to obtain all magnetic couplings, although their magnitude strongly depends on the exchange-correlation functional. Interestingly, a constant ratio between the magnetic coupling constants along a series of investigated functionals is found. This provides an additional equation to be used when relying on energy differences between spin states, which in turn allow solving the Heisenberg spectrum. The magnetic couplings thus obtained are compared to the experiment. Implications for the appropriate interpretation of the experiment and for the study of more complex systems are discussed.

Theoretical and computational investigation of meta-phenylene as ferromagnetic coupler in nitronyl nitroxide diradicals

We predict the magnetic exchange coupling constant (J) for 27 m-phenylene-based nitronyl nitroxide (NN) diradicals with nine different substituents in three unique (common ortho, ortho–meta and common meta) positions on the coupler unit by using the broken-symmetry density functional methodology. For all investigated diradicals, J values are computed using B3LYP, B3LYP-D3 and M06-2X functionals with 6–311+G(d,p) basis set. The JM06-2X value is larger than JB3LYP and closer to the observed value for the unsubstituted species. Substitutions at common ortho position always produce a greater angle of twist between the spin source and the coupler units. When the twist angle is very large, the nature of intramolecular magnetic interaction changes from ferromagnetic to antiferromagnetic. In these cases, the coupler–NN bond order becomes small. Substitution at the common meta position of m-phenylene in the diradical has little steric and hydrogen-bonding effects. Electron-withdrawing groups reveal a specific trend for single-atom substitution. An ortho substitution generally decreases J and a meta substitution always increases J with a decreasing −I effect. Variation of J with planarity as well as Hammett constant is investigated. The nucleus-independent chemical shift value is found to decrease from the corresponding mono-substituted phenyl derivatives. The dependence of J on these factors is explored.

Triplet–singlet gap in structurally flexible organic diradicals

A key factor in the search of high-spin ground state purely organic molecules concerns the effect of the inherent non-rigid structures on the magnetic and optical properties. This structural feature has not been properly addressed in previous theoretical works. Here, based on the experimentally characterized high-spin ground state of dendritic and star-branched polyradicals, we study four alternant hydrocarbon biradicals that intend to model these effects and, at the same time, provide a first step toward understanding more extended experimental structures. A series of density functional theory (DFT) and of wave function-based methods have been used to explore the richness of structural minima in the corresponding potential energy surfaces and to discuss its effect on the triplet–singlet gap of the proposed model systems. For a given model, the DFT-based B3LYP, M06-2X and MN-12SX methods provide a consistent description. Likewise, a multiconfigurational quasi-degenerate perturbation theory approach with the minimal π space as CASSCF reference is found to provide unbiased results. Despite the conformational richness found for these systems, they all can be described by a reduced set of values referred to only two structural parameters, being those the dihedral angles between the phenyl rings. For a given model, there is no significant change in the triplet–singlet gap depending on the chosen local minima.

Helical Folding-Induced Stabilization of Ferromagnetic Polyradicals Based on Triarylmethyl Radical Derivatives

Magnetic ordering in purely organic π-conjugated materials is a challenging, rare, and desirable event. The interest lies on the unique magnetic properties derived from high-spin carbon-based polymers/macromolecules tailored through appropriate synthetic routes. Ground-breaking achievements have been reported regarding magnetic ordering in an organic polymer using spin clusters as building blocks. This strategy leads to two-dimensional extended polyradicals with a concomitant loss of appealing macroscopic properties such as expected magnetic anisotropy in elongated shaped macromolecules containing carbon-bearing radicals. Here we provide compelling evidence of a secondary structure-induced stabilization of ferromagnetic polyradicals with robust magnetic properties and strongly suggest revisiting a discarded attempt to obtain polymeric linear-like radicals. An alternative synthetic approach is also proposed, based on polyradicals obtained from discrete molecular precursors (oligomers) long enough to ensure a secondary structure, rather than from polymerization processes.

Characterization of a Robust Co-II Fluorescent Complex Deposited Intact On HOPG

The new diimine fluorescent ligand ACRI-1 based on a central acridine yellow core is reported along with its coordination complex [Co2 (ACRI-1)2 ] (1), a fluorescent weak ferromagnet. Due to the strong fluorescence of the acridine yellow fluorophore, it is not completely quenched when the ligand is coordinated to Co(II) . The magnetic properties of bulk complex 1 and its stability in solution have been studied. Complex 1 has been deposited on highly ordered pyrolitic graphite (HOGP) from solution. The thin films prepared have been characterized by AFM, time-of-flight secondary ion mass spectrometry (TOF-SIMS), grazing incidence X-ray diffraction (GIXRD), X-ray absorption spectroscopy (XAS), X-ray magnetic circular dichroism (XMCD) and theoretical calculations. The data show that the complex is robust and remains intact on the surface of graphite.