TY - JOUR
T1 - Structural Characterization of Thermochromic and Spin Equilibria in Solid-State Ni(detu)4Cl2 (detu = N,N′-Diethylthiourea)
AU - Alfurayj, Ibrahim A.
AU - Young, Victor G.
AU - Jensen, Michael P.
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/2/15
Y1 - 2016/2/15
N2 - Consecutive thermochromic lattice distortional and spin crossover equilibria in solid-state Ni(detu)4Cl2 (detu = N,N′-diethylthiourea) are investigated by variable-temperature X-ray crystallography (173-333 K), DFT calculations, and differential scanning calorimetry. Thermochromism and anomalous magnetism were reported previously (S. L. Holt, Jr., et al. J. Am. Chem. Soc. 1964, 86, 519-520); the latter was attributed to equilibration of a singlet ground state and a thermally accessible triplet state, but structural data were not obtained. A crystal structure at 173(2) K revealed [Ni(detu)4]2+ centers with distorted planar ligation of nickel(II) to the four sulfur atoms, with an average Ni-S bond length of 2.226(3) Å. The nickel ion was displaced out-of-plane by 0.334 Å toward a proximal apical chloride at a nonbonding distance of 3.134(1) Å. Asymmetry in the trans S-Ni-S angles was coupled to a monoclinic tetragonal lattice distortion (T1/2 = 254 ± 11 K), resulting in thermochromism. Spin crossover occurs by tetragonal modulation of nickel(II) with approach of the proximal chloride at higher temperatures (T1/2 = 383 ± 18 K), which is consistent with a contraction of '0.096(4) Å in the Ni···Cl separation observed at 293 K. A high-spin (S = 1) square-pyramidal [Ni(dmtu)4Cl]+ model (dmtu = N,N′-dimethylthiourea) was optimized by DFT calculations, which estimated limiting equatorial Ni-S bond lengths of 2.45 Å and an apical Ni-Cl bond of 2.43 Å. Electronic spectra of the spin isomers were calculated by TD-DFT methods. Assignment of the FTIR spectrum was assisted by frequency calculations and isotope substitution.
AB - Consecutive thermochromic lattice distortional and spin crossover equilibria in solid-state Ni(detu)4Cl2 (detu = N,N′-diethylthiourea) are investigated by variable-temperature X-ray crystallography (173-333 K), DFT calculations, and differential scanning calorimetry. Thermochromism and anomalous magnetism were reported previously (S. L. Holt, Jr., et al. J. Am. Chem. Soc. 1964, 86, 519-520); the latter was attributed to equilibration of a singlet ground state and a thermally accessible triplet state, but structural data were not obtained. A crystal structure at 173(2) K revealed [Ni(detu)4]2+ centers with distorted planar ligation of nickel(II) to the four sulfur atoms, with an average Ni-S bond length of 2.226(3) Å. The nickel ion was displaced out-of-plane by 0.334 Å toward a proximal apical chloride at a nonbonding distance of 3.134(1) Å. Asymmetry in the trans S-Ni-S angles was coupled to a monoclinic tetragonal lattice distortion (T1/2 = 254 ± 11 K), resulting in thermochromism. Spin crossover occurs by tetragonal modulation of nickel(II) with approach of the proximal chloride at higher temperatures (T1/2 = 383 ± 18 K), which is consistent with a contraction of '0.096(4) Å in the Ni···Cl separation observed at 293 K. A high-spin (S = 1) square-pyramidal [Ni(dmtu)4Cl]+ model (dmtu = N,N′-dimethylthiourea) was optimized by DFT calculations, which estimated limiting equatorial Ni-S bond lengths of 2.45 Å and an apical Ni-Cl bond of 2.43 Å. Electronic spectra of the spin isomers were calculated by TD-DFT methods. Assignment of the FTIR spectrum was assisted by frequency calculations and isotope substitution.
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U2 - 10.1021/acs.inorgchem.5b02203
DO - 10.1021/acs.inorgchem.5b02203
M3 - Article
C2 - 26836378
AN - SCOPUS:84958811540
SN - 0020-1669
VL - 55
SP - 1469
EP - 1479
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 4
ER -