Correction: Blanco et al. Synthesis and Characterization of [Fe(Htrz)2(trz)](BF4)] Nanocubes. Molecules 2022, 27, 1213.

After publication of the paper [...].

Synthesis and Characterization of [Fe(Htrz)2(trz)](BF4)] Nanocubes.

Compounds that exhibit spin-crossover (SCO) type behavior have been extensively investigated due to their ability to act as molecular switches. Depending on the coordinating ligand, in this case 1H-1,2,4-triazole, and the crystallite size of the SCO compound produced, the energy requirement for the spin state transition can vary. Here, SCO [Fe(Htrz)2(trz)](BF4)] nanoparticles were synthesized using modified reverse micelle methods. Reaction conditions and reagent ratios are strictly controlled to produce nanocubes of 40-50 nm in size. Decreases in energy requirements are seen in both thermal and magnetic transitions for the smaller sized crystallites, where, compared to bulk materials, a decrease of as much as 20 °C can be seen in low to high spin state transitions.

Fe(II) Spin Transition Materials Including an Amino-Ester 1,2,4-Triazole Derivative, Operating at, below, and above Room Temperature.

A new family of one-dimensional Fe(II) 1,2,4-triazole spin transition coordination polymers for which a modification of anion and crystallization solvent can tune the switching temperature over a wide range, including the room temperature region, is reported. This series of materials was prepared as powders after reaction of ethyl-4H-1,2,4-triazol-4-yl-acetate (αEtGlytrz) with an iron salt from a MeOH/H2O medium affording: [Fe(αEtGlytrz)3](ClO4)2 (1); [Fe(αEtGlytrz)3](ClO4)2·CH3OH (2); [Fe(αEtGlytrz)3](NO3)2·H2O (3); [Fe(αEtGlytrz)3](NO3)2 (4); [Fe(αEtGlytrz)3](BF4)2·0.5H2O (5); [Fe(αEtGlytrz)3](BF4)2 (6); and [Fe(αEtGlytrz)3](CF3SO3)2·2H2O (7). Their spin transition properties were investigated by (57)Fe Mossbauer spectroscopy, superconducting quantum interference device (SQUID) magnetometry, and differential scanning calorimetry (DSC). The temperature dependence of the high-spin molar fraction derived from (57)Fe Mössbauer spectroscopy in 1 reveals an abrupt single step transition between low-spin and high-spin states with a hysteresis loop of width 5 K (Tc(↑) = 296 K and Tc(↓) = 291 K). The properties drastically change with modification of anion and/or lattice solvent. The transition temperatures, deduced by SQUID magnetometry, shift to Tc(↑) = 273 K and Tc(↓) = 263 K for (2), Tc(↑) = 353 K and Tc(↓) = 333 K for (3), Tc(↑) = 338 K and Tc(↓) = 278 K for (4), T(↑) = 320 K and T(↓) = 305 K for (5), Tc(↑) = 106 K and Tc(↓) = 92 K for (6), and T(↑) = 325 K and T(↓) = 322 K for (7). Annealing experiments of 3 lead to a change of the morphology, texture, and magnetic properties of the sample. A dehydration/rehydration process associated with a spin state change was analyzed by a mean-field macroscopic master equation using a two-level Hamiltonian Ising-like model for 3. A new structural-property relationship was also identified for this series of materials [Fe(αEtGlytrz)3](anion)2·nSolvent based on Mössbauer and DSC measurements. The entropy gap associated with the spin transition and the volume of the inserted counteranion shows a linear trend, with decrease in entropy with increasing the size of the counteranion. The first materials of this substance class to display a complete spin transition in both spin states are also presented.

Two-step spin transition in a 1D Fe(II) 1,2,4-triazole chain compound.

A thermochromic 1D spin crossover coordination (SCO) polymer [Fe(ßAlatrz)3](BF4)2⋅2 H2O (1⋅2 H2O), whose precursor ßAlatrz, (1,2,4-triazol-4-yl-propionate) has been tailored from a ß-amino acid ester is investigated in detail by a set of superconducting quantum interference device (SQUID), (57)Fe Mössbauer, differential scanning calorimetry, infrared, and Raman measurements. An hysteretic abrupt two-step spin crossover (T1/2(↓) = 230 K and T1/2(↑) = 235 K, and T1/2(↓) = 172 K and T1/2(↑) = 188 K, respectively) is registered for the first time for a 1,2,4-triazole-based Fe(II) 1D coordination polymer. The two-step SCO configuration is observed in a 1:2 ratio of low-spin/high-spin in the intermediate phase for a 1D chain. The origin of the stepwise transition was attributed to a distribution of chains of different lengths in 1⋅2 H2O after First Order Reversal Curves (FORC) analyses. A detailed DFT analysis allowed us to propose the normal mode assignment of the Raman peaks in the low-spin and high-spin states of 1⋅2 H2O. Vibrational spectra of 1⋅2 H2O reveal that the BF4(-) anions and water molecules play no significant role on the vibrational properties of the [Fe(ßAlatrz)3](2+) polymeric chains, although non-coordinated water molecules have a dramatic influence on the emergence of a step in the spin transition curve. The dehydrated material [Fe(ßAlatrz)3](BF4)2 (1) reveals indeed a significantly different magnetic behavior with a one-step SCO which was also investigated.

Peapod-type nanocomposites through the in situ growth of gold nanoparticles within preformed hexaniobate nanoscrolls.

A facile in situ method to grow Au nanoparticles (NPs) in hexaniobate nanoscrolls is applied to the formation of plasmonic Au@hexaniobate and bifunctional plasmonic-magnetic Au-Fe3 O4 @hexaniobate nanopeapods (NPPs). Utilizing a solvothermal treatment, rigid multiwalled hexaniobate nanoscrolls and partially filled Fe3 O4 @hexaniobate NPPs were first fabricated. These nanostructures were then used as templates for the controlled in situ growth of Au NPs. The resulting peapod structures exhibited high filling fractions and long-range uniformity. Optical measurements showed a progressive red shift in plasmonic behavior between Au NPs, Au NPPs, and Au-Fe3 O4 NPPs; magnetic studies found that the addition of gold in the Fe3 O4 @hexaniobate NPPs reduced interparticle coupling effects. The development of this approach allows for the routine bulk preparation of noble-metal-containing bifunctional nanopeapod materials.

Superparamagnetic iron oxide nanoparticles with variable size and an iron oxidation state as prospective imaging agents.

Magnetite nanoparticles in the size range of 3.2-7.5 nm were synthesized in high yields under variable reaction conditions using high-temperature hydrolysis of the precursor iron(II) and iron(III) alkoxides in diethylene glycol solution. The average sizes of the particles were adjusted by changing the reaction temperature and time and by using a sequential growth technique. To obtain γ-iron(III) oxide particles in the same range of sizes, magnetite particles were oxidized with dry oxygen in diethylene glycol at room temperature. The products were characterized by DLS, TEM, X-ray powder diffractometry, TGA, chemical analysis, and magnetic measurements. NMR r(1) and r(2) relaxivity measurements in water and diethylene glycol (for OH and CH(2) protons) have shown a decrease in the r(2)/r(1) ratio with the particle size reduction, which correlates with the results of magnetic measurements on magnetite nanoparticles. Saturation magnetization of the oxidized particles was found to be 20% lower than that for Fe(3)O(4) with the same particle size, but their r(1) relaxivities are similar. Because the oxidation of magnetite is spontaneous under ambient conditions, it was important to learn that the oxidation product has no disadvantages as compared to its precursor and therefore may be a better prospective imaging agent because of its chemical stability.

Synthesis of submicrometer hollow particles with a nanoscale double-layer shell structure.

The morphology of hollow, double-shelled submicrometer particles is generated through a rapid aerosol-based process. The inner shell is an essentially hydrophobic carbon layer of nanoscale dimension (20 nm), and the outer shell is a hydrophilic silica layer of approximately 40 nm, with the shell thickness being a function of the particle size. The particles are synthesized by exploiting concepts of salt bridging to lock in a surfactant (CTAB) and carbon precursors together with iron species in the interior of a droplet. This deliberate negation of surfactant templating allows a silica shell to form extremely rapidly, sealing in the organic species in the particle interior. Subsequent pyrolysis results in a buildup of internal pressure, forcing carbonaceous species against the silica wall to form an inner shell of carbon. The incorporation of magnetic iron oxide into the shells opens up applications in external stimuli-responsive nanomaterials.

The synthesis of mesoporous TiO2/SiO2/Fe2O3 hybrid particles containing micelle-induced macropores through an aerosol based process.

Mesoporous SiO(2)/TiO(2)/Fe(2)O(3) particles containing macropores of about 50 nm in diameter have been prepared by an aerosol process using cetyltrimethylammonium bromide (CTAB) as a templating agent. In contrast to the traditional templating effect of CTAB to form ordered mesoporous silicas, the morphology here is vastly different due to the presence of precursor iron salts. The particles have mesoporosity templated by CTAB but additionally have large voids leading to a combined macroporous and mesoporous structure. The morphology is explained through the formation of colloidal structures containing species such as CTA(+)X(-1)Fe(3+) colloids in the aerosol droplets, indicating of a salt bridging effect. This dual porosity has applied implications, as the macropores provide easy entry to the particle interior in potentially diffusion limited situations. Furthermore, the particles encapsulate Fe(2)O(3) and contain TiO(2) leading to the dual functional properties of magnetic response and photocatalytic activity.

Insights into the origin of cooperative effects in the spin transition of [Fe(NH2trz)3](NO3)2: the role of supramolecular interactions evidenced in the crystal structure of [Cu(NH2trz)3](NO3)2.H2O.

The thermally induced hysteretic spin transition (ST) that occurs in the polymeric chain compound [Fe(NH(2)trz)(3)](NO(3))(2) (1) above room temperature (T(c)(upward arrow) = 347 K, T(c)(downward arrow) = 314 K) has been tracked by (57)Fe Mössbauer spectroscopy, SQUID magnetometry, differential scanning calorimetry (DSC), and X-ray powder diffraction (XPRD) at variable temperatures. From the XRPD pattern indexation, an orthorhombic primitive cell was observed with the following cell parameters: a = 11.83(2) A, b = 9.72(1) A, c = 6.361(9) A at 298 K (low-spin state) and a = 14.37(2) A, b = 9.61(4) A, c = 6.76(4) A at 380 K (high-spin state). The enthalpy and entropy variation associated to the ST of 1, have been evaluated by DSC as DeltaH = 23(1) kJ mol(-1) and DeltaS = 69.6(1) J mol(-1) K(-1). These thermodynamic data were used within a two-level Ising like model for the statistical analysis of First Order Reversal Curve (FORC) diagram that was recorded for 1, in the cooling mode. Strong intramolecular cooperative effects are witnessed by the derived interaction parameter of J = 496 K. The crystal structure of [Cu(NH(2)trz)(3)](NO(3))(2).H(2)O (2) was obtained thanks to high quality single crystals prepared by slow evaporation after hydrothermal pretreatment. The catena poly[mu-tris(4-amino-1,2,4-triazole-N1,N2) copper(II)] dinitrate monohydrate (2) crystallizes in the monoclinic space group C2/c, with a = 16.635(6) A, b = 13.223(4) A, c = 7.805(3) A, beta = 102.56(3) degrees, Z = 4. Complex 2 is a 1D infinite chain containing triple N1,N2-1,2,4-triazole bridges with an intra-chain distance of Cu...Cu = 3.903(1) A. A dense H-bonding network with the nitrate counteranion involved in intra-chain and inter-chain interactions is observed. Such a supramolecular network could be at the origin of the unusually large hysteresis loop displayed by 1 (DeltaT approximately 33 K), as a result of an efficient propagation of elastic interactions through the network. This hypothesis is strengthened by the crystal structure of 2 and by the absence of crystallographic phase transition for 1 over the whole temperature range of investigation as shown by XRPD.

Transverse susceptibility method in nanoparticulate magnetic media.

Transverse susceptibility (TS) method is a reliable method for the determination of anisotropy in nanoparticulate media. To correctly evaluate the value of anisotropy in various modern nanostructured materials, a number of theoretical problems related to the method have to be well understood to avoid significant systematic errors. This paper presents the state of the art in the TS method which includes the expression for single domain particles with any type of anisotropy, the theoretical and micromagnetic, using Landau-Lifshitz-Gilbert (LLG) equation and stochastic LLG equation studies of the effects of ac field amplitude, inter-particle interactions, and magnetic relaxation. The problem of both real and imaginary parts of the TS signal is also discussed.

Interfacial adsorption and surfactant release characteristics of magnetically functionalized halloysite nanotubes for responsive emulsions.

Magnetically responsive oil-in-water emulsions are effectively stabilized by a halloysite nanotube supported superparamagnetic iron oxide nanoparticle system. The attachment of the magnetically functionalized halloysite nanotubes at the oil-water interface imparts magnetic responsiveness to the emulsion and provides a steric barrier to droplet coalescence leading to emulsions that are stabilized for extended periods. Interfacial structure characterization by cryogenic scanning electron microscopy reveals that the nanotubes attach at the oil-water interface in a side on-orientation. The tubular structure of the nanotubes is exploited for the encapsulation and release of surfactant species that are typical of oil spill dispersants such as dioctyl sulfosuccinate sodium salt and polyoxyethylene (20) sorbitan monooleate. The magnetically responsive halloysite nanotubes anchor to the oil-water interface stabilizing the interface and releasing the surfactants resulting in reduction in the oil-water interfacial tension. The synergistic adsorption of the nanotubes and the released surfactants at the oil-water interface results in oil emulsification into very small droplets (less than 20µm). The synergy of the unique nanotubular morphology and interfacial activity of halloysite with the magnetic properties of iron oxide nanoparticles has potential applications in oil spill dispersion, magnetic mobilization and detection using magnetic fields.

Synthesis and characterization of the rare-earth Dion-Jacobson layered perovskites, APrNb2O7 (A = Rb, Cs and CuCl).

The new double-layered perovskites, APrNb(2)O(7) (A = Rb, Cs) have been prepared by a high temperature ceramic method. Rietveld refinement of X-ray powder diffraction data confirmed the orthorhombic and tetragonal structures, respectively; RbPrNb(2)O(7) was refined in space group Imma (a = 5.4534(7) Å, b = 22.012(1) Å, c = 5.4549(7) Å) and CsPrNb(2)O(7) in P4/mmm (a = 3.8668(2) Å, c = 11.163(1) Å). (CuCl)PrNb(2)O(7), topochemically prepared by replacement of Rb(+)/Cs(+) with CuCl(+), contains a 2D Cu-Cl network between the PrNb(2)O(7) slabs (orthorhombic space group Pbam, a = 7.7328(6) Å, b = 7.7113(4) Å and c = 11.6706(3) Å). The parent compounds both show paramagnetic behavior µ(eff) (Rb) = 3.34(1)µ(B) and µ(eff) (Cs) = 3.60(2)µ(B) while the (CuCl)PrNb(2)O(7), paramagnetic (µ(eff) = 4.020(8)µ(B)) down to 20 K, exhibits antiferromagnet-like behavior below 20 K.

Effect of an oscillating magnetic field on the release properties of magnetic collagen gels.

The paper describes the effect of an oscillating magnetic field (OMF) on the morphology and release properties of collagen gels containing magnetic nanoparticles and microparticles and fluorescent drug analogues. Collagen gels were prepared through fibrillogenesis of collagen in the presence of iron oxide magnetic particles averaging 10 nm or 3 mum in diameter and rhodamine-labeled dextran (Dex-R) of molecular weights between 3000-70 000 g/mol. Dextran molecules effectively simulate protein-based drugs, since they have similar molecular weights and dimensions. The paper discusses the effect of an OMF on the release properties of the gels and proposes an empirical model to predict the release rate. It also demonstrates the self-repair capability of collagen gels following the structural damage caused by an OMF.