Structure and Magnetic Properties of Oxoverdazyl Radicals and Biradicals by an Integrated Computational Approach

Abstract

The structure, conformational behavior and magnetic properties of 1, 5-dimethyl-3-phenyl-6-oxoverdazyl radical and 1,1′,5,5′-tetramethyl-6, 6′-dioxo-3, 3′-biverdazyl biradical and of some related model compounds have been investigated by an integrated computational tool including an hybrid HF/DFT electronic method coupled to the polarizable continuum model for the description of solvent effects. The computed structural parameters are in agreement with the crystal structure for the radical and with refined post-HF computations for a simpler model compound. For the di-radical system a non planar structure is predicted both in vacuo and in solution.The nearly planar conformation found in the solid state can be ascribed to packing effect, as for the wellknown biphenyl molecule. The computed exchange coupling constant of the and 1, 1′, 5, 5′tetramethyl-6, 6′-dioxo-3, 3′-biverdazyl di-radical is in remarkable agreement with the experimental value when averaging effects of the inter-ring torsional motion are included in the calculations.

Intramolecular Spin Alignment in Photomagnetic Molecular Devices: A Theoretical Study

“…Regarding the verdazyl derivatives, there is a good agreement with both X‐ray data60 and previous calculations61 on systems containing the OV unit. In particular, when comparing calculated internal structure parameters of Dd 2 to experimental data60 (Table 2 and Table SI‐II), maximum deviations for bond lengths and angles (including a (N6‐C1 OV ‐N2)) are 0.03 Å and 2.0°, respectively.…”

A quantum mechanical study of TiCl3α, β and γ crystal phases: geometry, electronic structure and magnetism

“…2 reports a schematic illustration of relative orientations of the atomic S z for all Ti neighboring atoms in each broken symmetry state. 23,36 For each phase, the ferromagnetic (FM) solution consists of coherently oriented magnetic moments of all Ti atoms on fibers and layers, respectively.…”

Modified virtual orbitals for CI calculations of energy splitting in organic diradicals

“…19 It has been demonstrated 20 that the interference effects of some classes of electronic configurations may play an important role, so that variational CI calculations are to be preferred to perturbative methods. Both the DFT based [21][22][23][24][25] and the CI based 20,[26][27][28][29][30][31][32] methods have been applied to the computation of singlet-triplet gap in organic and inorganic diradicals.…”