Metal-thiolate bonding properties: single-crystal ESR, susceptibility, and polarized absorption evidence for a strong .pi. interaction in tetrakis(thiophenolato)cobaltate(II)

Magneto-Structural Correlations in a Series of Pseudotetrahedral [CoII(XR)4]2– Single Molecule Magnets: An ab Initio Ligand Field Study

“…27 Low temperature polarized vis-NIR spectra recorded with a 1% Co/Zn doped single crystal of a (Ph 4 P) 2 [Co/Zn(SPh) 4 ] mixture shows at least four sharp transitions in the region of 14 000−16 000 cm −1 . 22 However, at room temperature powder spectra, these lines are not well resolved ( Figure 6). …”

“…21 Later, single crystal susceptibility measurements gave more accurate values of D = −70(10) cm −1 , g ∥ = 2.7(1), and g ⊥ = 2.2(1), and the EPR on the doped single crystal with 10% Co/ Zn allowed one to estimate the rhombicity parameter E/D < 0.09. 22 Almost two decades later, Zadrozny et al showed that this compound exhibits slow magnetic relaxation without a magnetic bias field. They reported D = −74 cm −1 , E/D < 0.01, and g = 2.7(1), extracted from fitting of their low temperature (2−7 K) high-field (1−7 T) powder magnetization data.…”

“…It was shown for the SPh ligand 22 that the so-called misdirected valence should be taken into account. When for the sake of simplicity this is neglected, the AOM model leads to unphysical e πc parameters in our series with X = S, Se, and Te ( Table 2 in brackets).…”

Trinuclear Early/Late‐Transition‐Metal Thiolate Complexes

“…Assuming a three-spin system, nearly similar data can be obtained for 1 by considering either an anisotropy parameter D or a Weiss constant Θ W in the fittings (Table 1 2-with cobalt(II) in a distorted-tetrahedral environment (g | = 2.6 and g Ќ = 2.2). [55] For the six-coordinated vanadium(II) ion in the thiolato complex anion [V(SNC 5 H 4 ) 3 ]…”

Field-induced slow relaxation of magnetization in the S = 3/2 octahedral complexes trans-[Co{(OPPh2)(EPPh2)N}2(dmf)2], E = S, Se: effects of Co–Se vs. Co–S coordination

“…30 Complexes of Co(II) constitute the largest family of 3dmetal-based complexes showing slow relaxation of their magnetization. 22,31 It should be stressed that the tetrahedral S = 3/2 (PPh 4 ) 2 [Co(SPh) 4 ] complex 32,33 bearing a Co(II)S 4 core, was the first mononuclear 3d metal complex to exhibit slow relaxation of its magnetization in the absence of a Direct Current (DC) magnetic field. [34][35][36][37] Along these lines, tetrahedral [Co{(EP i Pr 2 ) 2 N} 2 ], E = S, 38 Se, 38 Te, 39 complexes, bearing dichalcogenidoimidodiphosphinato ligands 40 and Co(II)E 4 cores, exhibit slow relaxation of their magnetization, which was also observed in the absence of DC magnetic field for the E = Se, Te, complexes.…”