Under specific high concentration, high temperature conditions, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (MDFA) has been found to act as a very efficient source of difluorocarbene, exhibiting carbene reactivity characteristics comparable to those exhibited by trimethylsilyl 2,2-difluoro-2-(fluorosulfonyl)acetate (TFDA). For example, in reaction with highly unreactive n-butyl acrylate and using only 2 equiv of MDFA, a yield of 76% of difluorocyclopropane product was obtained after 2 days.
Strong magnetic couplings are generally observed intramolecularly in organic diradicals or in systems in which they are promoted by crystal engineering strategies involving, for example, transition metal ligation. We herein present a strong intermolecularly coupling verdazyl radical in the solid state without the use of such design strategies. The crystal structure of an acetylene-substituted verdazyl radical shows a unique antiparallel face-to-face orientation of the neighboring verdazyl molecules along with verdazyl-acetylene interactions giving rise to an alternating antiferromagnetic Heisenberg chain. Single crystal structural data at 80, 100, 173, and 223 K show that one of the π-stacking distances depends on temperature, while heat capacity data indicate the absence of a phase transition. Based on this structural input, broken symmetry DFT calculations predict a change from an alternating linear Heisenberg chain with two comparable coupling constants J and J at higher temperatures towards dominant pair interactions at lower temperatures. The predicted antiferromagnetic coupling is confirmed experimentally by magnetic susceptibility, solid-state EPR and NMR spectroscopic 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.
In all but the simplest crystal structures, the identification of all relevant interactions between magnetic sites as well as the setup of magnetic model spaces, which are necessary for modeling macroscopic magnetism, are tedious and error-prone tasks. Here, we present a procedure to generate magnetic susceptibility versus temperature curves using only a crystal structure as input. The procedure, which is based on the first-principles bottom-up approach [Deumal et al., J. Phys. Chem. A, 2002, 106, 1299], is designed in a way to require as little user interference as possible. We employ quantum chemical calculations to parametrize a Heisenberg Hamiltonian, which is set up and diagonalized for different magnetic model spaces to ensure convergence of the model. We apply the procedure to several 6-oxo-verdazyl radical structures, including newly synthesized compounds, and compare the results to data we obtained from magnetic susceptibility measurements as well as published data to further benchmark our procedure. Furthermore, the different impact of certain dominating coupling constants is systematically analyzed.
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