TY - JOUR
T1 - Intercalation of 3X-pyridine with X = F, Cl, Br, I, in 2D ferrous nitroprusside. Thermal induced spin transition in Fe(3F-pyridine)2[Fe(CN)5NO]
AU - Avila, Y.
AU - Crespo, P. M.
AU - Plasencia, Y.
AU - Mojica, H. R.
AU - Rodríguez-Hernández, J.
AU - Reguera, E.
N1 - Publisher Copyright:
© 2020 Elsevier Inc.
PY - 2020/6
Y1 - 2020/6
N2 - The series of 2D solids, Fe(3XPy)2[Fe(CN)5NO] with 3X = 3-Fluoro, 3-Chloro, 3-Bromo, 3-Iodo and Py = Pyridine, was obtained by intercalation of the organic molecule (3XPy) between neighboring layers of 2D ferrous nitroprusside. The organic ligand was found coordinated to the axial positions for the iron atom linked at the equatorial N ends of the CN groups in the nitroprusside building block, [Fe(CN)5NO]. The axial CN and NO ligands remain unlinked and contribute to the solid stability through attractive dipole-dipole interactions. The formed hybrid solids preserve the 2D nature because no chemical bond is established between neighboring organic molecules in the interlayer region. For X = F, a thermal induced spin transition was observed, but not for the remaining derivatives. The nature of such behavior is discussed according to the recorded XRD, Raman and Mössbauer data and computational calculations. The spin crossover transition in Fe(3FPy)2[Fe(CN)5NO] is an incomplete process, a sample fraction of about 50% remains in paramagnetic state, even at 5 K. The spin transition is accompanied of an atypical small structural change, corresponding to a variation of 0.7% for the unit cell volume. Such behavior finds explanation in both, the bonding properties of the N end of the CN ligands in the nitroprusside pseudo-octahedral block, and in the intermolecular interactions in the interlayer region.
AB - The series of 2D solids, Fe(3XPy)2[Fe(CN)5NO] with 3X = 3-Fluoro, 3-Chloro, 3-Bromo, 3-Iodo and Py = Pyridine, was obtained by intercalation of the organic molecule (3XPy) between neighboring layers of 2D ferrous nitroprusside. The organic ligand was found coordinated to the axial positions for the iron atom linked at the equatorial N ends of the CN groups in the nitroprusside building block, [Fe(CN)5NO]. The axial CN and NO ligands remain unlinked and contribute to the solid stability through attractive dipole-dipole interactions. The formed hybrid solids preserve the 2D nature because no chemical bond is established between neighboring organic molecules in the interlayer region. For X = F, a thermal induced spin transition was observed, but not for the remaining derivatives. The nature of such behavior is discussed according to the recorded XRD, Raman and Mössbauer data and computational calculations. The spin crossover transition in Fe(3FPy)2[Fe(CN)5NO] is an incomplete process, a sample fraction of about 50% remains in paramagnetic state, even at 5 K. The spin transition is accompanied of an atypical small structural change, corresponding to a variation of 0.7% for the unit cell volume. Such behavior finds explanation in both, the bonding properties of the N end of the CN ligands in the nitroprusside pseudo-octahedral block, and in the intermolecular interactions in the interlayer region.
KW - Intercalation compounds
KW - Layered ferrous nitroprusside
KW - Spin crossover behavior
KW - Thermal induced spin transition
UR - http://www.scopus.com/inward/record.url?scp=85081124659&partnerID=8YFLogxK
U2 - 10.1016/j.jssc.2020.121293
DO - 10.1016/j.jssc.2020.121293
M3 - Artículo
SN - 0022-4596
VL - 286
JO - Journal of Solid State Chemistry
JF - Journal of Solid State Chemistry
M1 - 121293
ER -