Magnetic interactions in thiazyl-based magnets: The role of the charge and spin densities
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Otros documentos de la autoría: Campo, Javier; Alberola Catalán, Antonio; Palacio, Fernando; Luzon, Javier; Goeta, Andres E.; Rawson, Jeremy M.; McIntyre, Garry J.
Metadatos
Mostrar el registro completo del ítemcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
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Título
Magnetic interactions in thiazyl-based magnets: The role of the charge and spin densitiesAutoría
Fecha de publicación
2008Editor
International Union of CrystallographyISSN
01087673Tipo de documento
info:eu-repo/semantics/articleVersión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
The crystal structure of the organic radical p-O2NC6F4CNSSN was
determined at 20 K through a single-crystal neutron-diffraction
experiment. It crystallises in the tetragonal space group P41212,
unchanged from a ... [+]
The crystal structure of the organic radical p-O2NC6F4CNSSN was
determined at 20 K through a single-crystal neutron-diffraction
experiment. It crystallises in the tetragonal space group P41212,
unchanged from a previous single-crystal X-ray diffraction
experiment at 220 K although there are some changes in molecular
geometry and intermolecular contacts arising from the contraction
of the unit cell. Polarized neutron diffraction at 1.5 K revealed that
the spin distribution is predominantly localised on the N and S
atoms of the heterocyclic ring with a small negative spin density
on the heterocyclic C atom. Spin populations determined using a
multipolar analysis were -0.06, +0.25 and +0.28 on the C, N and S
sites, respectively. These spin populations are in excellent agreement
with both ab-initio DFT calculations (spin populations on the C, N
and S sites of -0.07, 0.22 and 0.31, respectively) and cw-EPR studies
which estimated the spin population on the N site as 0.24. The DFT
calculated spin density revealed less than 1% spin delocalisation
onto the perfluoroaryl ring, several orders of magnitude lower than
the density on the heterocyclic ring. cw-ENDOR studies at both
X-band (9 GHz) and Q-band (34 GHz) frequencies probed the spin
populations at the two chemically distinct F atoms. These spin
populations on the F atoms ortho and meta to the dithiadiazolyl
ring are of magnitude 10-3 and 10-4 respectively. Additional high-resolution single-crystal X-ray diffraction studies at 100 K analysed
within the atoms-in-molecules (AIM) framework gave detailed
information on the charge density distribution [-]
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