Co(II) chemistry of 2,6-bis(2-pyridylcarbonyl)pyridine: an icosanuclear Co cluster exhibiting superparamagnetic relaxation.

High-nuclearity transition-metal complexes (clusters) are of special interest in chemistry and physics because, both in terms of size and physical properties, they bridge the gap between the microscopic and macroscopic world, and between quantum and classical systems. In terms of size, the smallest classical nanoparticles fabricated today are the same size as the largest metal clusters that are synthesized by bottom-up methods. In terms of physical properties, certain transition-metal clusters exhibit single-molecule magnetism at low temperatures, that is, they retain their magnetization in zero field in a manner analogous to that of classical macroscopic magnets, but at the same time they …

Raman spectroscopy of the high- and low-spin states of the spin crossover complex Fe(phen)2(NCS)2: an initial approach to estimation of vibrational contributions to the associated entropy change

Abstract Raman spectra of the spin-crossover complex Fe(phen)2(NCS)2 in the solid state have been recorded at 785 nm as a function of temperature to investigate the contribution of intramolecular vibrations to the entropy change, ΔS, associated with spin crossover. The modes of major interest for estimating the contribution lie in the range 100–500 cm−1, where the largest qualitative changes with temperature in the Raman spectra were observed. Analysis of these data, with the working assumption of an average frequency in this range as representative of the 15 distortion modes of an idealised FeN6 octahedron, leads to the conclusion that the intramolecular vibrations represent a primary cont…

A Diferrous Single‐Molecule Magnet

The diferrous complex [Fe2(acpypentO)(NCO)3] (1),(acpypentO– = the anion of 1,5-bis[2-pyridyl(1-ethylimino)]pentane-3-ol) was studied by spectroscopic (dual-mode X-band EPR and 57Fe-Mossbauer) and magnetic (AC magnetic susceptibility) techniques. Complex 1 (A. K. Boudalis et al., Inorg. Chem.2004, 43, 1574) was previously shown to exhibit an intramolecular ferromagnetic coupling with important single-ion anisotropies with marked differences in the single-ion electronic parameters of the two iron sites. In this contribution, additional studies are carried out to probe its dynamic magnetic properties. Mossbauer spectra recorded at liquid helium temperatures indicate slow paramagnetic relaxati…

Structural Transformations and Magnetic Effects Induced by Solvent Exchange in the Spin Crossover Complex [Fe(bpp) 2 ][Cr(bpy)(ox) 2 ] 2

Structural, thermal, magnetic and solvent-exchange properties of the spin crossover compound [Fe(bpp)2][Cr(bpy)(ox)2]2 containing paramagnetic anions are given. This complex salt 1 crystallises as a dihydrate with two inequivalent (high-spin and low-spin) FeII sites. The dehydrated compound is a spin-crossover material with T1/2 ↑ = 369 K and T1/2 ↓ = 353 K. Rehydration takes place without loss of crystallinity, yielding a polymorph (2) with 100 % high-spin Fe II sites. The different high-spin fractions in 1 and 2 have been correlated to structural changes in the FeII second coordination sphere. The magnetic response to the presence of different sorbed molecules has also been explored. © Wi…

A Nonanuclear Iron(II) Single-Molecule Magnet

A family of enneanuclear iron(II) single-molecule magnets.

Complexes [Fe 9 (X) 2 -(02CMe)8{(2-py) 2 CO 2 } 4 ] (X - = OH (1), N 3 - (2), and NCO- (3)) have been prepared by a route previously employed for the synthesis of analogous Co 9 and Ni 9 complexes, involving hydroxide substitution by pseudohalides (N 3 - , NCO-). As indicated by DC magnetic susceptibility measurements, this substitution induced higher ferromagnetic couplings in complexes 2 and 3, leading to higher ground spin states compared to that of 1. Variable-field experiments have shown that the ground state is not well isolated from excited states, as a result of which it cannot be unambiguously determined. AC susceptometry has revealed out-of-phase signals, which suggests that these…