Intramolecular Exchange Coupling Research Articles

Metaphenylene-Based Nitroxide Diradicals: A Protocol To Calculate Intermolecular Coupling Constant in a One-Dimensional Chain

Intramolecular magnetic exchange coupling constants are determined for seven isolated metaphenylene-based dinitroxide diradicals by unrestricted density functional methodology (UDFT) using a number of hybrid functionals such as B3LYP, B3LYP-D3, M06-2X, HSE, and LC-ωPBE. Geometry optimizations for both triplet and broken symmetry solutions are performed with the 6-311G(d,p) basis set for all the molecules. In all cases, B3LYP somewhat overestimates the coupling constant, and M06-2X produces a more realistic value. The range-separated HSE and LC-ωPBE functional yield large deviations from experiment. The nature of spin coupling agrees with the spin alternation rule and the calculated spin densities, in conjunction with the McConnell rule. It can also be explained in terms of the nondisjoint Single Occupied Molecular Orbital effect. Furthermore, it correlates with the calculated NICS(1) isotropic and zz and hyperfine coupling constants. We also put forward a method for the determination of the intramolecular (J) and intermolecular (J') coupling constants from quantum chemical calculations on a one-dimensional chain of weakly bound diradicals. Two expressions are derived for the energies of different spin states in terms of J and J'. Exemplary UDFT computations are done on the N-mers (N = 2-6) of two diradicals for which the crystal coordinates are available. The intramolecular and intermolecular coupling constants are determined from the calculated UDFT energies. These are indeed in general agreement with the measured coupling constants.

Understanding the Magnetic Anisotropy in a Family of N23– Radical-Bridged Lanthanide Complexes: Density Functional Theory and ab Initio Calculations

Density functional theory (DFT) and ab initio methods were used to investigate the influence of both intramolecular exchange coupling and single-ion anisotropy on the relaxation barriers of a series of N2(3-) radical-bridged lanthanide complexes [{[(Me3Si)2N]2(THF)Ln}2(μ-η(2):η(2)-N2)](-) (Ln = Gd(III) (1), Tb(III) (2), Dy(III) (3), Ho(III) (4), and Er(III) (5)) reported by Long and co-workers. DFT calculations show that the exchange coupling between the lanthanide ions is very weak, but the Ln-N2(3-) coupling is strong for each complex. Moreover, the exchange couplings of Ln-N2(3-) are antiferromagnetic for Ln = Gd(III), Tb(III), Dy(III), and Ho(III) but ferromagnetic for Er(III) for the nearly orthogonal magnetic orbitals on Er(III) and N2(3-). Ab initio calculations show that both of the large magnetic anisotropy of single Tb fragment and the strong Tb-N2(3-) antiferromagnetic couplings lead to the largest energy barrier of complex 2. Although the energy barrier of a single Er fragment is the second largest, the relaxation barrier of complex 5 is only 36.0 cm(-1) due to the weak Er(III)-N2(3-) coupling. This study suggests that both intramolecular exchange coupling and single-ion anisotropy contribute greatly to the full relaxation barrier of lanthanide-based single-molecule magnets (SMMs), which expands the understanding of SMMs using only the giant-spin model.

Theoretical Investigation of Stilbene as Photochromic Spin Coupler

Density functional theory (DFT) based calculations are used here to investigate the magnetic behavior, spectroscopic transitions, and possible photomagnetic properties of stilbene derivatives using photochromicity of cis- and trans-forms of the parent molecule. Nitronyl nitroxide (NN), iminonitroxide (IN), tetrathiafulvalene cation (TTF), and verdazyl (VER) are used as monoradical centers at the p, p' positions. The B3LYP functional with the usual broken symmetry approach and a sufficiently large basis set is chosen to obtain reliable estimates of the intramolecular exchange coupling constants (J). It is found that, with stilbene as a spacer, the coupling of TTF with NN, IN, and VER is always antiferromagnetic with J being generally large and negative. Although J values obtained for cis- and trans-forms are both negative, the difference in J values is quite large. Spectroscopic transition energies and corresponding oscillator strengths of cis- and trans-stilbene diradicals are estimated by time-dependent (TD)-DFT calculations using the same functional. Interestingly, the spectral features of the diradicals are similar to those of cis- and trans-stilbene, which suggests that stilbene diradicals would have good photoswitching properties. Finally, we show that, when these diradicals are placed in a matrix, photochromicity would be accompanied by a significant change in paramagnetic susceptibility.

Electronic and magnetic properties of molecule-metal interfaces: Transition-metal phthalocyanines adsorbed on Ag(100)

We present a systematic investigation of molecule-metal interactions for transition-metal phthalocyanines (TMPc, with TM = Fe, Co, Ni, Cu) adsorbed on Ag(100). Scanning tunneling spectroscopy and density functional theory provide insight into the charge transfer and hybridization mechanisms of TMPc as a function of increasing occupancy of the 3d metal states. We show that all four TMPc receive approximately one electron from the substrate. Charge transfer occurs from the substrate to the molecules, inducing a charge reorganization in FePc and CoPc, while adding one electron to ligand \pi-orbitals in NiPc and CuPc. This has opposite consequences on the molecular magnetic moment: in FePc and CoPc the interaction with the substrate tends to reduce the TM spin, whereas in NiPc and CuPc an additional spin is induced on the aromatic Pc ligand, leaving the TM spin unperturbed. In CuPc, the presence of both TM and ligand spins leads to a triplet ground state arising from intramolecular exchange coupling between d and \pi electrons. In FePc and CoPc the magnetic moment of C and N atoms is antiparallel to that of the TM. The different character and symmetry of the frontier orbitals in the TMPc series leads to varying degrees of hybridization and correlation effects, ranging from the mixed-valence (FePc, CoPc) to the Kondo regime (NiPc, CuPc). Coherent coupling between Kondo and inelastic excitations induces finite-bias Kondo resonances involving vibrational transitions in both NiPc and CuPc and triplet-singlet transitions in CuPc.

Ligand-Driven Exchange Coupling in ${\rm Mn}_{4}$ Single-Molecule Magnets

Distorted cubane [Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4+</sup> Mn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3+</sup> (μ <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> -L <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2-</sup> ) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> (μ <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> -X <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-</sup> )(Z) <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3-</sup> (dbm) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-</sup> ] ( L=O; X=various; Z=(OAc) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> ; dbmH=dibenzoyl-methane) single-molecule magnets (SMMs) have been studied by first-principles calculations. Our earlier studies showed that the basic mechanism of antiferromagnetic Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4+</sup> -Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3+</sup> coupling ( <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">J</i> <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">AB</sub> ) is determined by the π type hybridization among the <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">d</i> <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">z</sub> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> orbitals at the Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3+</sup> sites and the <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">t</i> <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2g</sub> orbitals at the Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4+</sup> site through the <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">p</i> orbitals at the μ <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> -L <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2-</sup> ions. This result allows us to predict that ferrimagnetic structure of Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4+</sup> Mn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3+</sup> molecules will be the most stable with the Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4+</sup> -(μ <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> -L <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2-</sup> )-Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3+</sup> angle α ≈ 90 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">°</sup> , while synthesized Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4+</sup> Mn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3+</sup> molecules have α ≈ 95 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">°</sup> . One approach is suggested to design new Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4+</sup> Mn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3+</sup> SMMs having a much more stable ferrimagnetic state. This approach is controlling the Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4+</sup> -(μ <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> -L <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2-</sup> )-Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3+</sup> exchange pathways by rational variations in ligands to strengthen the hybridization between Mn ions. In this paper, by combining variations in the L and Z ligands, ten new high-spin [Mn <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4+</sup> Mn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3+</sup> (μ <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> -L <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2-</sup> ) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> (μ <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> -F <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-</sup> ) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> (Z) <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3-</sup> (CH(CHO) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> ) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-</sup> ] ( L=NCGeH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> , NGeCH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> , NGe <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> , NSiGeH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> , or NGeSiH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> ; Z=(OAc) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> or MeC(CH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> NCOMe) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> ) molecules have been designed. Our calculated results show that these ten modelling Mn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> molecules have α ≈ 90 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">°</sup> and <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">J</i> <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">AB</sub> / <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">k</i> <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">B</sub> in the range of (-231.6, -147.4) K, in which the molecule with [L,Z]=[NCGeH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> ,MeC(CH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> NCOMe) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> ] has the highest <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">J</i> <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">AB</sub> / <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">k</i> <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">B</sub> of - 231.6 K corresponding to α = 89.23 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">°</sup> . This value is over 3 times larger than that of synthesized Mn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> SMMs. Our calculated results demonstrate combining variations in the L and Z ligands as an effective way to tailor intramolecular exchange coupling of the Mn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> molecules. The results would give some hints for synthesizing new SMMs.

Spin coupling and relaxation inside molecule–metal contacts

Advances in molecular electronics depend on the ability to control the charge and spin of single molecules at the interface with a metal. Here we show that bonding of metal-organic complexes to a metallic substrate induces the formation of coupled metal-ligand spin states, increasing the spin degeneracy of the molecules and opening multiple spin relaxation channels. Scanning tunnelling spectroscopy reveals the sign and magnitude of intramolecular exchange coupling as well as the orbital character of the spin-polarized molecular states. We observe coexisting Kondo, spin, and vibrational inelastic channels in a single molecule, which lead to pronounced intramolecular variations of the conductance and spin dynamics. The spin degeneracy of the molecules can be controlled by artificially fabricating molecular clusters of different size and shape. By comparing data for vibronic and spin-exchange excitations, we provide a positive test of the universal scaling properties of inelastic Kondo processes having different physical origin.

Towards designing Mn 4 molecules with strong intramolecular exchange coupling

Distorted cubane Mn 4+ Mn 3+ 3 single-molecule magnets (SMMs) have been studied by first-principles calculations, i.e. [Mn 4 L 3 X(OAc)3(dbm)3] (L=O; X=F, Cl, and Br; dbmH=dibenzoyl-methane). It was shown in our previous paper (Tuan et al 2009 Phys. Chem. Chem. Phys. 11 717) that the ferrimagnetic structure of Mn 4+ Mn 3+ 3 SMMs is dominated by π type hybridization between the d z 2 orbitals at the three high-spin Mn 3+ ions and the t 2g orbitals at the Mn 4+ ion. To design new Mn 4+ Mn 3+ 3 molecules having much more stable ferrimagnetic states, one approach is suggested. This involves controlling the Mn 4+–L–Mn 3+ exchange pathways by rational variations in ligands to strengthen the hybridization between the Mn ions. Based on this method, we succeed in designing new distorted cubane Mn 4+ Mn 3+ 3 molecules having Mn 4+–Mn 3+ exchange coupling of about 3 times stronger than that of the synthesized Mn 4+ Mn 3+ 3 molecules. These results give some hints regarding experimental efforts to synthesize new superior Mn 4+ Mn 3+ 3 SMMs.

A DFT Study on the Magnetostructural Property of Ferromagnetic Heteroverdazyl Diradicals with Phenylene Coupler

We have theoretically designed five different m-phenylene coupled high-spin bis-heteroverdazyl diradicals and their analogous p-phenylene coupled low-spin positional isomers. The geometry-based aromaticity index, harmonic oscillator model of aromaticity (HOMA) values for both the couplers (local HOMA), and the whole diradicals (global HOMA) have been calculated for all the diradicals. We also qualitatively relate these HOMA values with the intramolecular magnetic exchange coupling constants (J), calculated using a broken symmetry approach within unrestricted density functional theory framework. Structural aromaticity index HOMA of linkage specific benzene rings in our designed diradical systems shows that the aromatic character depends on the planarity of the molecule and it controls the sign and magnitude of J. The predicted J values are explained on the basis of spin polarization maps, average dihedral angles, and magnetic orbitals. The effect of the spin leakage phenomenon on magnetic exchange coupling constant and that on HOMA values of certain phosphaverdazyl systems has been explicitly discussed. In addition, a similar comparison is made between the calculated exchange coupling constants and corresponding HOMA values. The main novelty of this work stands on the consideration of the aromatic behavior by means of the geometrical index HOMA. We also estimate another aromaticity index, nucleus independent chemical shift (NICS) values for the phenylene coupler in each diradical to measure aromaticity and compare its value with that of HOMA. The ground state stabilities of these diradicals have also been compared.

One-Dimensional Coordination Polymers from Hexanuclear Manganese Carboxylate Clusters Featuring a {MnII4MnIII2(μ4-O)2} Core and Spacer Linkers

The bridging of hexanuclear mixed-valent carboxylate coordination clusters of the type [Mn(6)O(2)(O(2)CR)(10)] (R = CMe(3); CHMe(2)) featuring a {Mn(II)(4)Mn(III)(2)(mu(4)-O)(2)} core by geometrically rigid as well as flexible spacer ligands such as pyrazine (pyz), nicotinamide (na), or 1,2-bis(4-pyridyl)ethane (bpe) results exclusively in one-dimensional (1D) coordination polymers. The formation of {[Mn(6)O(2)(O(2)CCMe(3))(10)(Me(3)CCO(2)H)(EtOH)(na)] x EtOH x H(2)O}(n) (1), {[Mn(6)O(2)(O(2)CCHMe(2))(10)(pyz)(3)] x H(2)O}(n) (2), and {[Mn(6)O(2)(O(2)CCHMe(2))(10)(Me(2)CHCO(2)H)(EtOH)(bpe)] x Me(2)CHCO(2)H}(n) (3) illustrates a surprising preference of the interlinked {Mn(6)} units toward 1D coordination chains. In the solid-state, the observed chain propagation axes are either colinear (1 and 3) or perpendicular (2), whereby crystal packing is further influenced by solvent molecules. Magnetic properties of these network compounds can be rationalized based on that the magnetism of discrete [Mn(6)O(2)(O(2)CR)(10)]-type coordination clusters with all-antiferromagnetic intramolecular exchange and weak antiferromagnetic intercluster coupling in 1, 2, and 3 follows the expected exchange coupling strength of the employed spacer linkers.

Very Strongly Ferromagnetically Coupled Diradicals from Mixed Radical Centers. II. Nitronyl Nitroxide Coupled to Tetrathiafulvalene via Spacers

We predict large and positive intramolecular magnetic exchange coupling constants (J) for coupled diradicals constructed from nitronyl nitroxide and tetrathiafulvalene monoradical moieties. These diradicals have the general formula TTF-coupler-NN, where the couplers are mostly aromatic systems. Unrestricted density functional methodology (UB3LYP) has been used to optimize the molecular geometries of the triplet diradicals using the 6-311 g(d,p) basis set. This has been followed by single-point UB3LYP calculations for triplet and broken symmetry (BS) states using 6-311++g(3df,3pd) basis and the optimized triplet geometries. We find that the species comprising of ethylene (geminal coupling) and pyridine as couplers have singlet ground states whereas the other species have triplet ground states. These findings are in support of the spin alternation rule. The largest J value we predict is 648.6 cm(-1) for the molecule with the spacer pyrrole. We also determine the percent weightings of triplet and singlet components in the BS state, estimate the diradical nature, and calculate the relative weights of different singlet and triplet component functions in the BS solution in each case.

Diphenoxido‐Bridged CoII and ZnII Complexes of Tripodal N2O2 Ligands: Stabilisation of MII‐Coordinated Phenoxyl Radical Species

AbstractThree new tripodal ligands with an N2O2 donor set, namely2‐tert‐butyl‐6‐({(2‐hydroxybenzyl)[2‐(2‐pyridyl)ethyl]amino}methyl)‐4‐methylphenol (H2L1), 2‐tert‐butyl‐6‐({(2‐hydroxybenzyl)[2‐(2‐pyridyl)ethyl]amino}methyl)‐4‐methoxyphenol (H2L2) and 2‐tert‐butyl‐6‐({[2‐(dimethylamino)ethyl](2‐hydroxybenzyl)amino}methyl)‐4‐methoxyphenol (H2L3) have been synthesised. Treatment of the ligands with Co(CH3CO2)2·4H2O or [Zn(H2O)6][ClO4]2 in the presence of Et3N provides the corresponding CoII and ZnII complexes of composition [MII2(L1)2] [M = Co (1) (single‐crystals are a solvate with the composition [CoII2(L1)2]·2CHCl3, i.e. 1·2CHCl3); M = Zn (2)], [MII2(L2)2] [M = Co (3); Zn (4)] and [CoII2(L3)2] (5). Crystallographic analyses reveal that the complexes have closely similar diphenoxido‐bridged structures. Each metal centre assumes MIIN2O3 coordination. The geometry around each metal ion in 1·2CHCl3 (τ = 0.76), 2 (τ = 0.77), 3 (τ = 0.74), 4 (τ = 0.76) and 5 [one CoII (τ = 0.49) and the other CoII (τ = 0.63)] is intermediate between ideal square‐pyramidal (τ = 0) and trigonal‐bipyramidal (τ = 1). Temperature‐dependent magnetic studies reveal weak intramolecular antiferromagnetic exchange couplings for all the three CoII complexes(–J = 1.84, 1.32 and 5.70 cm–1 for 1, 3 and 5, respectively). Spectroscopic properties of the complexes have also been investigated. Cyclic voltammetric (CV) measurements of 1 and 2 show an irreversible oxidative response at Epa (anodic peak potential) in the range 0.60–0.75 V relative to the SCE (saturated calomel electrode), whereas two successive quasi‐reversible oxidative responses can be observed for 3–5 at E1/2 values in the range 0.40–0.53 V relative to the SCE. Oxidative responses are due to the formation of MII‐coordinated phenoxyl radical species. The metal‐coordinated phenoxyl radical species, generated by two‐electron coulometric oxidation of 3–5, were characterised by CV and by adsorption and EPR spectroscopy. The stability of such species was determined by measuring the decay constant (absorption spectroscopy), which reveals that the phenoxyl radical species of 5 is more stable than that of 3 and 4. EPR spectroscopic studies (120 K) of coulometrically generated two‐electron oxidised species of 4 in CH2Cl2 (containing 0.1 M TBAP) at 298 K reveal a combination of an isotropic S = ${1 \over 2}$ signal at g = 2 [(phenolato)(phenoxyl radical)‐coordinated dizinc(II) complex] and a spin‐triplet resonance (S = 1) that gives rise to the symmetric split‐line pattern [bis(phenoxyl radical)‐cordinated dizinc(II) complex]. To pinpoint the site of oxidation (metal‐ or ligand‐centred) in each case, DFT calculations were performed at the B3LYP level of theory.

Intramolecular ferromagnetic coupling in bis-oxoverdazyl and bis-thioxoverdazyl diradicals with polyacene spacers

We predict the intramolecular exchange coupling constant (J) for 10 different oxo- and thioxo-verdazyl-based hi-spin ground-state diradicals with linear polyacene couplers of varying length using the broken symmetry approach in an unrestricted DFT framework. The magnetic characteristics of these systems are explained using the spin-density distribution, and an analysis is made by “magnetic” orbitals. The nuclear independent chemical shift (NICS) values have been calculated for the diradicals. The average NICS(1) (1 A above the ring surface) value per benzenoid ring increases as the size of the coupler increases. So-called ΔNICS(1) values [the difference among average NICS(1) per benzenoid ring in the coupler and the NICS(1) of the linear polyacene molecule] are correlated with J values. Bond orders and hyperfine coupling constants have also been evaluated and analyzed for the diradicals.

Synthesis, crystal structures and magnetic properties of a new radical NIT-1′-MeBzIm and the corresponding complexes of Ni(II), Co(II) and Zn(II) containing NIT-1′-MeBzIm

Abstract A new chelating radical ligand NIT-1′-MeBzIm (1) (NIT-1′-MeBzIm = 2-{2′-[(l’-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) and three corresponding complexes [M(NIT-1′-MeBzIm)2(NO3)(CH3OH)]·(NO3)(CH3OH) (M = Ni (2), Co (3)), [Zn(NIT-1′-MeBzIm)2(CH3OH)2]·(ClO4)2(H2O)2(CH3OH) (4) have been prepared and structurally characterized by X-ray diffraction method and variable-temperature magnetic susceptibility measurements. In the crystal structures, radical 1, complexes 3 and 4 crystallize isomorphously in monoclinic, with the space groups are P2(1)/n, P2(1)/c, and P2(1), respectively. Complex 2 crystallizes in orthorhombic space group Pna2(1). The metal ions of the three complexes embed in distorted octahedron geometry centers and coordinated by two NIT-1′-MeBzIm radicals from the equatorial positions to form trans configuration, the axial positions are occupied by one methanol molecule and one nitrate anion for 2 and 3, but by two methanol molecules for 4. Magnetic measurement demonstrates that the intramolecular exchange couplings in 2 and 3 are antiferromagnetic with J = −41.25 and −38.1 cm−1, where the spin Hamiltonian is defined as Ĥ = −2J(Ŝrad1 ŜM + ŜM Ŝrad2) based on the molecular structure of radical-metal-radical, while that in 4 is weak ferromagnetic with J = 1.65 cm−1 where the spin Hamiltonian is defined as Ĥ = −2JŜ1Ŝ2 within the complexes. Intermolecular exchange couplings in 1 is also weak ferromagnetic with J = 1.32 cm−1 where the spin Hamiltonian is defined as Ĥ = −2JŜ1Ŝ2 between radical and radical. Compounds 2–4 exhibit intermolecular antiferromagnetic interaction with the zJ′ = −0.52 cm−1, θ = −0.75 K and zJ′ = −0.49 cm−1 for compounds 2, 3 and 4, respectively, which should ascribe to the weak interactions. The crystal structures for 1–4 have intermolecular hydrogen bonding interactions (and π–π piling interactions for 1 and 3) which form the single crystals into 1-D, 2-D, 3-D structures and seems to play an important role in molecular packing and in magnetic coupling.

On magnetic nature of Mn clusters

Manganese atom having number of unpaired electrons appears as a strong building block for molecular magnets. This prompts the investigation of the magnetic behavior of Mn based clusters. In this work, we have studied the magnetic characteristics of neutral Mn dimer, charged Mn dimer and its oxide. The magnetic characteristics of the chosen systems have been quantified in terms of intramolecular exchange coupling constant. The computation is performed in the framework of density functional theory using broken symmetry approach. We obtain positive values of magnetic exchange coupling constants for all these three species and hence their ferromagnetic ground states are recognized. Direct exchange of spins between the sets of d-electrons in the metals is found responsible for the ferromagnetic behavior of these clusters. In case of Mn 2O −, super exchange, another possible exchange mechanism, is barred due to unavailability of vacant metal d-orbitals. Dependence of exchange coupling constant on intermetallic distance is also studied taking these Mn clusters as reference, which shows a maximum value of coupling constant in the proximity of equilibrium bond distance.

Density Functional Theory Based Study of Magnetic Interaction in Bis-Oxoverdazyl Diradicals Connected by Different Aromatic Couplers

We design and investigate 11 different bis-oxoverdazyl diradicals connected by various aromatic couplers for their magnetic properties. The intramolecular magnetic exchange coupling constants (J) have been calculated using a broken symmetry approach in DFT framework. The J values are explained using spin polarization maps and magnetic orbitals. Isotropic hyperfine coupling constants (hfcc's) have been calculated for all the species in vacuum. The computed hfcc values also support intramolecular magnetic interactions. It has been found that some of the diradicals have ferromagnetic character while the others are antiferromagnetic in nature.

Very Strongly Ferromagnetically Coupled Diradicals from Mixed Radical Centers: Nitronyl Nitroxide Coupled to Oxoverdazyl via Polyene Spacers

We predict extremely large and positive intramolecular magnetic exchange coupling constants (J) for coupled diradicals constructed from nitronyl nitroxide (NN) and oxoverdazyl (o-VER). These radicals have the general formula o-VER(N)-nC-NN where nC represents an olefinic spacer with n = 0, 2, 4, 6, and 8. Species like o-VER(C)-nC-NN have negative coupling constants. The atoms in the parentheses show the point of attachment of the coupler to the verdazyl moiety. Both the N-linked series and C-linked series have comparable stability. The triplet molecular geometries were optimized by the density functional (UB3LYP) method using the 6-311 g(d,p) basis set. This was followed by single-point UB3LYP calculations using 6-311++g(3df,3pd) basis. To calculate J, single-point broken-symmetry computations were performed on the optimized triplet geometries and using the same basis set. The N-linked diradicals coupled through conjugated polyenes are topologically different. These are found to have coupling constants of the order of 1000 cm(-1), whereas the C-linked diradicals show coupling constants of the order of -100 cm(-1). In general, for both cases, the absolute magnitude of the coupling constant decreases with the increase in the length of the spacer.

Reaching Optimal Light‐Induced Intramolecular Spin Alignment within Photomagnetic Molecular Device Prototypes

Ground-state (GS) and excited-state (ES) properties of novel photomagnetic molecular devices (PMMDs) are investigated by means of density functional theory. These organic PMMDs undergo a ferromagnetic alignment of their intramolecular spins in the lowest ES. They are comprised of: 1) an anthracene unit (An) as both the photosensitizer (P) and a transient spin carrier (SC) in the triplet ES ((3)An*); 2) imino-nitroxyl (IN) or oxoverdazyl (OV) stable radical(s) as the dangling SC(s); and 3) bridge(s) (B) connecting peripheral SC(s) to the An core at positions 9 and 10. Improving the efficiency of the PMMDs involves strengthening the ES intramolecular exchange coupling (J(ES)) between transient and persistent SCs, hence the choice of 2-pyrimidinyl (pm) as B elements to replace the original p-phenylene (ph). Dissymmetry of the pm connectors leads to [SC-B-P-B-SC] regio-isomers int. and ext., depending on whether the pyrimidinic nitrogen atoms point towards the An core or the peripheral SCs, respectively. For the int. regio-isomers we show that the photoinduced spin alignment is significantly improved because the J(ES)/k(B) value is increased by a factor of more than two compared with the ph-based analogue (J(ES)/k(B)>+400 K). Most importantly, we show that the optimal J(ES)/k(B) value ( approximately +600 K) could be reached in the event of an unexpected saddle-shaped structural distortion of the lowest ES. Accounting for this intriguing behavior requires dissection of the combined effects of 1) borderline intramolecular steric hindrance about key An-pm linkages, which translates into the flatness of the potential energy surface; 2) spin density disruption due to the presence of radicals; and 3) possibly intervening photochemistry, with An acting as a light-triggered electron donor while pm, IN, and OV behave as electron acceptors. Finally, potentialities attached to the [(SC)-pm-An-pm](int) pattern are disclosed.

Magnetic properties of Cr 2O n− clusters: A theoretical study

The chromium ions in each of the chromium oxide cluster anions Cr 2O −, Cr 2O 2 − and Cr 2O 3 − have been found to be ferro-magnetically coupled to each other. In each case, one of the highest spin states is the ground state. In fact, the ground states correspond to the spin multiplicities 10, 10 and 8, respectively. The magnetic interaction proceeds via super exchange mechanism. The intra-molecular ferromagnetic exchange coupling constant is estimated from the density functional methodology using broken symmetry approach. It is found to decrease steadily with increasing number of oxygen atoms. A rationale for this phenomenon can be given from molecular orbital analysis.

Searching for the Exchange Shift: a Set of Test Systems

We suggest that intramolecular exchange coupling J in solutions can possibly be measured with just a ruler using an analogue of the nuclear magnetic resonance paramagnetic shift. If one of the two coupled electron spins is rapidly relaxing, the resulting electron paramagnetic resonance (EPR) spectrum of the system is the resolved spectrum for the second spin with a shifted g-factor. The amount and the sense of the shift are both linear in J, which thus can be obtained from the measured shift by simple algebra. We prepared a set of complexes of rare-earth ions with nitroxides to probe this idea, but the sought effect was not yet found indicating J < 0.1 cm−1 for these systems. Either the radical centers should be brought closer to the central lanthanide ion, or the ion itself should be substituted for a rapidly relaxing transition-metal ion, e.g., Cr2+ or Co2+. Furthermore we report evolving EPR spectra that reflect the inner life of the complexes in solution.

Towards understanding of magnetic interactions within a series of tetrathiafulvalene–π conjugated-verdazyl diradical cation system: a density functional theory study

The intramolecular magnetic exchange coupling constants (J) for a series of tetrathiafulvalene (TTF) and verdazyl diradical cations connected by a range of pi conjugated linkers have been investigated by means of methodology based on unrestricted density functional theory. The magnetic interaction between radicals is transmitted via pi-electron conjugation for all considered compounds. The calculation of J yields strong or medium ferromagnetic coupling interactions (in the range of 56 and 300 K) for diradical cations connected by linkers with an even number of carbon atoms that are able to provide a spin polarization pathway, while antiferromagnetic coupling is predicted when linkers with an odd number of carbon atoms are employed. The topological analysis of spin density distributions have been used to reveal the effects of the spin polarization on both linkers and spin carriers. The absence of heteroatoms that impede the spin polarization pathway, and the existence of a unique spin polarization path instead of several possible competitive routes are factors which contribute to large positive J values favoring ferromagnetic interactions between the two terminal pi-radicals. The magnitude of J depends strongly on the planarity of the molecular structure of the diradical cation since a more effective orbital overlap between the two pi-systems can be achieved. Hence, the dependence of J on the torsion angle (theta) of each spin carrier has been analyzed. In this respect, our findings show that this geometrical distortion reduces largely the calculated J values for ferromagnetic couplings, leading to weak antiferromagnetic interactions for a torsion angle of 90 degrees .