Spin Crossover in Double Salts Containing Six- and Four-Coordinate Cobalt(II) Ions

Joanna Palion-Gazda; Barbara Machura; Rafal Kruszynski; Thais Grancha; Nicolás Moliner; Francesc Lloret; Miguel Julve

doi:10.1021/acs.inorgchem.7b00360

Spin Crossover in Double Salts Containing Six- and Four-Coordinate Cobalt(II) Ions

Inorg Chem. 2017 Jun 5;56(11):6281-6296. doi: 10.1021/acs.inorgchem.7b00360. Epub 2017 May 22.

Authors

Joanna Palion-Gazda¹, Barbara Machura¹, Rafal Kruszynski², Thais Grancha³, Nicolás Moliner³, Francesc Lloret³, Miguel Julve³

Affiliations

¹ Department of Crystallography, Institute of Chemistry, University of Silesia , Ninth Szkolna Street, 40006 Katowice, Poland.
² Department of X-ray Crystallography and Crystal Chemistry, Institute of General and Ecological Chemistry, Lodz University of Technology , 116 Żeromski Street, 90-924 Łódź, Poland.
³ Departament de Química Inorgànica/Instituto de Ciencia Molecular (ICMol), Universitat de València , C/Catedrático José Beltrán 2, 46980 Paterna, València, Spain.

PMID: 28530402
DOI: 10.1021/acs.inorgchem.7b00360

Abstract

The preparation and spectroscopic and structural characterization of three cobalt(II) complexes of formulas [Co(tppz)₂](dca)₂ (1), [Co(tppz)₂][Co(NCS)₄]·MeOH (2), and [Co(tppz)₂][Co(NCO)₄]·2H₂O (3) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine and dca = dicyanamide] are reported here. Compounds 1-3 have in common the presence of the cationic [Co(tppz)₂]²⁺ entity where each mer-tridentate tppz ligand coordinates to the cobalt(II) ion equatorially through two pyridyl donors and axially via the pyrazine, completing the six-coordination. The electroneutrality is achieved by the organic dca group (1) and the anionic tetrakis(thiocyanato-κN)cobaltate(II) (2) and tetrakis(cyanato-κN)cobaltate(II) (3) complexes. Direct current (dc) magnetic susceptibility measurements of 1 in the temperature range 1.9-400 K show the occurrence of a thermally induced spin crossover behavior of the [Co(tppz)₂]²⁺ unit from a high spin (S = 3/2) at higher temperatures to a low-spin (S = 1/2) at lower temperatures, with the low spin phase being reached at T ≤ 200 K. X-band electron paramagnetic resonance (EPR) measurements in solution at low temperatures were used to characterize the low spin state. An analytical expression based on the combination of the spin-orbit coupling and both first- and second-order Zeeman effects for a d⁷ electronic configuration was used to fit the magnetic data of 1, the values of the best-fit parameters being C_vib = 0.1367(9), λ = -168(2) cm^-1, α = 1.12(1), Δ = 1626(15) cm^-1, and g_LS = 2.12(1). The magnetic behavior of the four-coordinate cobalt(II) ions [Co(NCS)₄]^2- (2) and [Co(NCO)₄]^2- (3) with a ⁴A₂ ground state overlaps with the spin crossover of the [Co(tppz)₂]₂₊ entity, the abrupt decrease of the χ_MT product below 15.0 K being due to zero-field splitting effects between the spin components |±1/2> and |±3/2>. The combined analysis of the dc magnetic data and the Q-band EPR spectra in the solid state of 2 and 3 led to the following sets of best-fit parameters: C_vib = 0.105(5), λ = -170(4) cm^-1, α = 1.10(2), Δ = 1700(25) cm^-1, g_LS = 2.10(1), g_HS = 2.27(1), and |D| = 3.80(2) cm^-1 (2) and C_vib = 0.100(1), λ = -169(5) cm^-1, α = 1.10(3), Δ = 1500(30) cm^-1, g_LS = 2.10(1), g_HS = 2.28(1), and |D| = 4.30(2) cm^-1 (3). Some evidence of slowing of the relaxation of the magnetization has been found in the out-of-phase ac signal at very low temperatures under applied dc fields of 0.1-0.4 T for 3, suggesting the occurrence of single-ion magnet behavior of its [Co(NCO)₄]^2- anionic entity.