Steric Quenching of Mn(III) Thermal Spin Crossover: Dilution of Spin Centers in Immobilized Solutions

Structural and magnetic properties of a new spin crossover complex [Mn(4,6-diOMe-sal2323)]+ in lattices with ClO4−, (1), NO3−, (2), BF4−, (3), CF3SO3−, (4), and Cl− (5) counterions are reported. Comparison with the magnetostructural properties of the C6, C12, C18 and C22 alkylated analogues of the ClO4− salt of [Mn(4,6-diOMe-sal2323)]+ demonstrates that alkylation effectively switches off the thermal spin crossover pathway and the amphiphilic complexes are all high spin. The spin crossover quenching in the amphiphiles is further probed by magnetic, structural and Raman spectroscopic studies of the PF6− salts of the C6, C12 and C18 complexes of a related complex [Mn(3-OMe-sal2323)]+ which confirm a preference for the high spin state in all cases. Structural analysis is used to rationalize the choice of the spin quintet form in the seven amphiphilic complexes and to highlight the non-accessibility of the smaller spin triplet form of the ion more generally in dilute environments. We suggest that lattice pressure is a requirement to stabilize the spin triplet form of Mn3+ as the low spin form is not known to exist in solution.

Radical Scavenging Activity and Pharmacokinetic Properties of Coumarin–Hydroxybenzohydrazide Hybrids

Free radicals often interact with vital proteins, violating their structure and inhibiting their activity. In previous studies, synthesis, characterisation, and the antioxidative properties of the five different coumarin derivatives have been investigated. In the tests of potential toxicity, all compounds exhibited low toxicity with significant antioxidative potential at the same time. In this paper, the radical scavenging activity of the abovementioned coumarin derivatives towards ten different radical species was investigated. It was found that all investigated compounds show good radical scavenging ability, with results that are in correlation with the results published in the previous study. Three additional mechanisms of radical scavenging activity were investigated. It was found that all three mechanisms are thermodynamically plausible and in competition. Interestingly, it was found that products of the Double Hydrogen Atom Transfer (DHAT) mechanism, a biradical species in triplet spin state, are in some cases more stable than singlet spin state analogues. This unexpected trend can be explained by spin delocalisation over the hydrazide bridge and phenolic part of the molecule with a low probability of spin pairing. Besides radical-scavenging activity, the pharmacokinetic and drug-likeness of the coumarin hybrids were investigated. It was found that they exhibit good membrane and skin permeability and potential interactions with P-450 enzymes. Furthermore, it was found that investigated compounds satisfy all criteria of the drug-likeness tests, suggesting they possess a good preference for being used as potential drugs.

Quasi-isotropic SMMs: slow relaxation of the magnetization in polynuclear CuII/MnII complexes.

Three field induced SMMs built from quasi isotropic cations like CuII and MnII have been characterized, showing that relatively large clusters with quasi negligible D and different ground spin state,...

Vapor-triggered Reversible Crystal Transformation in Nickel-based Magnetic Molecular Switch

Vapor-trigged crystal to crystal transformation between a discrete trinuclear complex [Ni3(sih)2(py)8] and a two-dimensional (2D) coordination polymer [Ni3(sih)2(py)2]n·DMF·H2O was demonstrated. It provides an example of solid-state coordination induced spin state...

Evidence for surface effects on the intermolecular interactions in Fe(ii) spin crossover coordination polymers

From X-ray absorption spectroscopy (XAS) and X-ray photoemission spectroscopy (XPS) it is evident that the spin state transition behavior of Fe(ii) spin crossover coordination polymer crystallites at the surface differs from the bulk.

FeIII in a high-spin state in bis(5-bromosalicylaldehyde 4-ethylthiosemicarbazonato-κ3 O,N 1,S)ferrate(III) nitrate monohydrate, the first example of such a cationic FeIII complex unit

The synthesis and crystal structure (100 K) of the title compound, [Fe(C10H11BrN3OS)2]NO3·H2O, is reported. The asymmetric unit consists of an octahedral [FeIII(HL)2]+ cation, where HL − is H-5-Br-thsa-Et or 5-bromosalicylaldehyde 4-ethylthiosemicarbazonate(1−) {systematic name: 4-bromo-2-[(4-ethylthiosemicarbazidoidene)methyl]phenolate}, a nitrate anion and a noncoordinated water molecule. Each HL − ligand binds via the thione S, the imine N and the phenolate O atom, resulting in an FeIIIS2N2O2 chromophore. The ligands are orientated in two perpendicular planes, with the O and S atoms in cis and the N atoms in trans positions. This [Fe(HL)2](anion)·H2O compound contains the first known cationic FeIII entity containing two salicylaldehyde thiosemicarbazone derivatives. The FeIII ion is in the high-spin state at 100 K. In addition, a comparative IR spectroscopic study of the free ligand and the ferric complex is presented, demonstrating that such an analysis provides a quick identification of the degree of deprotonation and the coordination mode of the ligand in this class of metal compounds. The variable-temperature magnetic susceptibility measurements (5–320 K) are consistent with the presence of a high-spin FeIII ion with a zero-field splitting D = 0.439 (1) cm−1.