Synthesis and Reactivity of a Neutral Homocyclic Silylene.

Isolation of the neutral homocyclic silylene 2 is possible via amine ligand abstraction with potassium graphite (KC8 ) and subsequent reaction with SiMe3 Cl from a bicyclic silicon(I) amide J. This reaction proceeds via an anionic homoaromatic silicon ring compound 1 as an intermediate. The twofold-coordinated silicon atom in the homocyclic silylene 2 is stabilized by an allyl-type π-electron delocalization. 2 reacts in an oxidative addition with two equivalents of MeOH and in cycloadditions with ethene, phenylacetylene, diphenylacetylene and with 2,3-dimethyl-1,3-butadiene to afford novel functionalized ring compounds.

Electronic effects in profluorescent benzotriazinyl radicals: a combined experimental and theoretical study.

The synthesis, photophysical characterization, and quantum chemical calculations of a series of benzotriazinyl radicals and their styryl radical trapping products are presented. The benzotriazinyl radicals are non-luminescent but surprisingly the corresponding styryl radical trapping products exhibit high fluorescence quantum yields (up to 60% in some cases), making them highly valuable probes or labels. Additionally, the influence of the substitution pattern on the optical properties of the radical trapping products was observed experimentally and interpreted by means of quantum chemical calculations. Specific substitution patterns showed a bathochromic shift compared to the unsubstituted compound. Computationally, it was shown that this substitution pattern leads to a stronger energetic stabilization of the lowest unoccupied molecular orbital than the highest occupied molecular orbital. Analysis of the influence of the substitution pattern on the optical properties showed a bathochromic shift in several examples, which was interpreted by means of quantum chemical calculations.

Subsystem density-functional theory for interacting open-shell systems: spin densities and magnetic exchange couplings.

We investigate the possibility of describing interacting open-shell systems in high-spin and broken-symmetry (BS) states with subsystem density-functional theory (sDFT). This subsystem method typically starts from the electronic-structure results obtained for individual systems, for which the spin states can be individually defined. Through the confining effect of the embedding potential and/or the use of monomer basis sets, these individual spin states can be preserved in sDFT calculations. This offers the possibility of easy convergence to broken-symmetry states with arbitrary local spin patterns. We show that the resulting spin densities are in very good agreement with successfully converged broken-symmetry Kohn-Sham density-functional theory (KS-DFT) calculations. Yet sDFT can even cure those BS cases where KS-DFT suffers from convergence problems or convergence to undesired spin states. In contrast to KS-DFT, the sDFT-results only show a mild exchange-correlation functional dependence. We also show that magnetic coupling constants from sDFT are not satisfactory with standard approximations for the non-additive kinetic energy. When this component is evaluated "exactly", i.e. based on potential reconstruction, however, the magnetic coupling constants derived from spin-state energy differences are greatly improved. Hence, the interacting radicals studied here represent cases where even (semi-)local approximations for the non-additive kinetic-energy potential work well, while the parent energy functionals do not yield satisfactory results for spin-state energy differences.

Antiferromagnetic ordering based on intermolecular London dispersion interactions in amphiphilic TEMPO ammonium salts.

Antiferromagnetic coupling in TEMPO-based radicals can be enhanced via self-assembly through London dispersion interactions in amphiphilic solids. The synthesis, magnetic characterization, and three crystal structures of the solid radical ion salts (R-DMAT-n)X with various counterions X and alkyl chain lengths n are reported. Magnetic susceptibility and absolute EPR signal intensity measurements show singlet-triplet transitions in a number of cases, which is discussed in relation to the crystal structures. Antiferromagnetic ordering effects are sensitive to both the length of the alkyl chain and the counter anion.

Towards reliable references for electron paramagnetic resonance parameters based on quantum chemistry: the case of verdazyl radicals.

We present an efficient and accurate computational procedure to calculate properties measurable by EPR spectroscopy. We simulate a molecular dynamics (MD) trajectory by employing the quantum mechanically derived force field (QMDFF) [S. Grimme, J. Chem. Theory Comput., 2014, 10, 4497] and sample the trajectory at different time steps. For each snapshot EPR properties are calculated with a hybrid density functional theory (DFT) method. EPR spectra are simulated based on the averaged results. We applied the strategy to a number of previously published and novel verdazyl radicals, for which we recorded EPR spectra. The resulting simulated spectra are compatible with experiment already before employing an additional fitting step, in contrast to those from single point electronic-structure calculations. After the refinement, the experimental data are excellently reproduced, and the fitted EPR parameters do not deviate much from the calculated ones. This provides confidence in ascribing a direct physical meaning to the refined data in terms of experimental EPR parameters rather than merely considering them as mathematical fit parameters. We also find that couplings to hydrogen nuclei have a significant influence on the spectra of verdazyl radicals.

Cooperative Magnetism in Crystalline N-Aryl-Substituted Verdazyl Radicals: First-Principles Predictions and Experimental Results.

We report on a series of eight diaryl-6-oxo-verdazyl radicals containing a tert-butyl group at the C(3) position with regard to their crystal structure and magnetic properties by means of magnetic susceptibility measurements in combination with quantum chemical calculations using a first-principles bottom-up approach. The latter method allows for a qualitative prediction and detailed analysis of the correlation between the solid-state architecture and magnetic properties. Although the perturbation in the molecular structure by varying the substituent on the N-aryl ring may appear small, the effects upon the structural parameters controlling intermolecular magnetic coupling interactions are strong, resulting in a wide spectrum of cooperative magnetic behavior. The non-substituted 1,5-diphenyl-tert-butyl-6-oxo-verdazyl radical features a ferromagnetic one-dimensional spin ladder type magnetic network-an extremely rarely observed phenomenon for verdazyl radicals. By varying substituents at the phenyl group, different non-isostructural compounds were obtained with widely different magnetic motifs ranging from linear and zigzag one-dimensional chains to potentially two-dimensional networks, from which we predict magnetic susceptibility data that are in qualitative agreement with experiments and reveal a large sensitivity to packing effects of the molecules. The present study advances the fundamental understanding between solid-state structure and magnetism in organically based radical systems.