TY - JOUR
T1 - Spin-crossover in [Fe(Quinazoline)2][Fe(CN)5NO]. Evidence of its framework flexibility
AU - Avila, Y.
AU - Scanda, K.
AU - Sánchez, L.
AU - Mojica, R.
AU - Divó-Matos, Y.
AU - Mendoza, F.
AU - Rodríguez-Hernández, J.
AU - Reguera, E.
N1 - Publisher Copyright:
© 2023 Elsevier B.V.
PY - 2023/5/1
Y1 - 2023/5/1
N2 - The titled material shows a thermally induced spin-crossover (SCO) in the 75–150 K temperature region, with a narrow hysteresis of about 3 K. The recorded DSC data show a similar small hysteresis. Such behavior suggests that its framework has high flexibility, making possible the reversible spin transition on the sample cooling and warming, with slight kinetic effects. The crystal structure of this material was solved and refined from powder XRD patterns, complemented with information from IR, Raman, TG, and Mössbauer data. It crystallizes with a monoclinic unit cell in the P21 space group. Its framework is formed by stacked [Fe(Quinazoline)2][Fe(CN)5NO] layers. The organic molecule occupies the axial coordination sites for the iron atom linked to the N ends of equatorial CN ligands. In the interlayer region, organic ligands from adjacent layers remain coupled through weak dipolar and dispersive forces and a π⋅⋅⋅π interaction. Such relatively weak forces between adjacent layers explain the high framework flexibility inferred from the magnetic and DSC data. The crystal structure for the low temperature (low spin) phase was obtained by periodic DFT calculations using the VASP package. The results herein discussed contribute to understanding the role of the solid framework flexibility on the spin-crossover behavior in Hofmann-like 2D coordination polymers.
AB - The titled material shows a thermally induced spin-crossover (SCO) in the 75–150 K temperature region, with a narrow hysteresis of about 3 K. The recorded DSC data show a similar small hysteresis. Such behavior suggests that its framework has high flexibility, making possible the reversible spin transition on the sample cooling and warming, with slight kinetic effects. The crystal structure of this material was solved and refined from powder XRD patterns, complemented with information from IR, Raman, TG, and Mössbauer data. It crystallizes with a monoclinic unit cell in the P21 space group. Its framework is formed by stacked [Fe(Quinazoline)2][Fe(CN)5NO] layers. The organic molecule occupies the axial coordination sites for the iron atom linked to the N ends of equatorial CN ligands. In the interlayer region, organic ligands from adjacent layers remain coupled through weak dipolar and dispersive forces and a π⋅⋅⋅π interaction. Such relatively weak forces between adjacent layers explain the high framework flexibility inferred from the magnetic and DSC data. The crystal structure for the low temperature (low spin) phase was obtained by periodic DFT calculations using the VASP package. The results herein discussed contribute to understanding the role of the solid framework flexibility on the spin-crossover behavior in Hofmann-like 2D coordination polymers.
KW - 2D coordination polymer
KW - DFT calculation
KW - Ferrous nitroprusside
KW - Hofmann-like solid
KW - Spin transition
KW - Spin-crossover
UR - http://www.scopus.com/inward/record.url?scp=85146944345&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2023.121402
DO - 10.1016/j.ica.2023.121402
M3 - Artículo
AN - SCOPUS:85146944345
SN - 0020-1693
VL - 549
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
M1 - 121402
ER -