“…Also staying within the intramolecular context, QTM cannot fully account for such a situation either. Indeed, low out-of-phase signals can still be the case even under dc magnetic fields aimed at suppressing QTM [54][55][56][57][58].…”
Ac susceptometry and magnetic hysteresis studies are the two most used techniques for the basic characterization of magnetic relaxation properties of Single-Molecule Magnets. Nevertheless, the full quantitative treatment of such studies is rarely carried out, in particular as regards the absolute magnitudes of the in-phase (χʹ) and out-of-phase (χʺ) ac susceptibility signals, and the exact shapes of hysteresis loops. To facilitate such quantitative analyses, an SMM evaluator tool has been developed. It uses the dc magnetic susceptibility/magnetization properties of any SMM, and the parameters characteristic of the various relevant relaxation processes (Orbach, Raman, Direct, QTM) to calculate the exact ac susceptibility/magnetic hysteresis curves under any temperature, magnetic field and ac frequency or dc field scan rate. It also implements a model that calculates the actual fraction of molecules that contribute to the SMM effect, as well as models which account for distributions of the relaxation times. Indicative examples of a "strong", a "medium" and a "weak" SMM are analysed with this tool, demonstrating the additional information that can be extracted by quantitative treatment of such data.
“…Also staying within the intramolecular context, QTM cannot fully account for such a situation either. Indeed, low out-of-phase signals can still be the case even under dc magnetic fields aimed at suppressing QTM [54][55][56][57][58].…”
Ac susceptometry and magnetic hysteresis studies are the two most used techniques for the basic characterization of magnetic relaxation properties of Single-Molecule Magnets. Nevertheless, the full quantitative treatment of such studies is rarely carried out, in particular as regards the absolute magnitudes of the in-phase (χʹ) and out-of-phase (χʺ) ac susceptibility signals, and the exact shapes of hysteresis loops. To facilitate such quantitative analyses, an SMM evaluator tool has been developed. It uses the dc magnetic susceptibility/magnetization properties of any SMM, and the parameters characteristic of the various relevant relaxation processes (Orbach, Raman, Direct, QTM) to calculate the exact ac susceptibility/magnetic hysteresis curves under any temperature, magnetic field and ac frequency or dc field scan rate. It also implements a model that calculates the actual fraction of molecules that contribute to the SMM effect, as well as models which account for distributions of the relaxation times. Indicative examples of a "strong", a "medium" and a "weak" SMM are analysed with this tool, demonstrating the additional information that can be extracted by quantitative treatment of such data.
“…For 1 the axial type spectrum spectrum is partially, but clearly resolved with spectroscopic splitting factors gꓕ = 2.06, g‖ = 2.28 and parallel hyperfine splitting parameter A‖ = 175 G, resulting from the interaction of the unpaired electron of Cu(II) with the spin of copper nucleus I = 3/2. It is identical for both natural isotopes of 63 Cu and 65 Cu, so eight hyperfine levels can be expected with four allowed transitions: MS=±1 and MI= 0 (Figure S19). 110 The axial EPR spectrum of compound 2 exhibits similar values of spectroscopic splitting parameters gꓕ = 2.06 and g‖ = 2.25 but with no hyperfine structure.…”
Section: Cw-epr and Pulsed Epr Studiesmentioning
confidence: 97%
“…At the same time Titiš and co-workers 64 reported the first example of a mononuclear d 8 hexacoordinate Ni(II) complex [Ni(pydc)(pydm)] (pydc = pyridine-2,6-dicarboxylate, pydm = 2,6-bis(hydroxymethyl) pyridine), demonstrating that low coordination number geometries are not a prerequisite for SIM behavior. Bhowmick et al 65 reported first example of SIM behavior in d 7 Ni(III; S = ½) complexes. Cui 66 introduced a new approach, where slow magnetic relaxation originates from the low spin state of d 7 Co(II; S = ½) ions.…”
Current advances in molecular magnetism are aimed at the construction of molecular nanomagnets and spin qubits for their utilization as high-density data storage materials and quantum computers. Mononuclear coordination compounds with low spin values of S=½ are excellent candidates for this endeavour, but their construction via rational design is limited. This particularly applies to the single copper(II) spin center, having been only recently demonstrated to exhibit slow relaxation of magnetisation in the appropriate octahedral environment. We have thus prepared a novel, modular organic scaffold that would allow one to gain general insight into how purposeful structural differences affect the slow magnetic relaxation in monometallic, transition metal complexes. As a proof-of-principle, we demonstrate how one can construct two, structurally very similar complexes with isolated Cu(II) ions in an octahedral ligand environment, the magnetic properties of which differ significantly. The differences in structural symmetry effects and in magnetic relaxation are corroborated with a series of experimental and theoretical techniques, showing how symmetry distortions affect the relaxation behaviour in these isolated Cu(II) systems. Our highly modular organic platform can be efficiently utilized for the construction of various transition-metal ion systems in the future, effectively providing a model system for investigation of magnetic relaxation via targeted structural distortions.
“… 1 , 16 Diamagnetic dilution is achieved by taking a magnetic molecule and either (1) dissolving it into an organic solvent or matrix (as was done for Mn 12 O 12 ), 17 , 18 or (2) cocrystallization with a structurally analogous, closed-shell species. For example, mononuclear M 2+ complexes can be diluted with Zn 2+ 19 or low-spin Ni 2+ analogues 20 ; M 3+ species can be diluted with low-spin Co 3+ , 21 Y 3+ , 22 , 23 or Ga 3+ 24 ; and M 4+ species can be diluted with Ti 4+ . 25 In these dilute systems, wherein the size advantage of high-density molecular information storage is lost, magnetic relaxation is often slowed by several orders of magnitude.…”
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