Inducing Ferrimagnetic Exchange in 1D-FeSe2 Chains Using Heteroleptic Amine Complexes: [Fe(en)(tren)][FeSe2]2.

[Fe(en)(tren)][FeSe2]2 (en = ethylenediamine, C2H8N2, tren = tris(2-aminoethyl)amine, C6H18N4) has been synthesized by a mixed-ligand solvothermal method. Its crystal structure contains heteroleptic [Fe(en)(tren)]2+ complexes with distorted octahedral coordination, incorporated between 1D-FeSe2 chains composed of edge-sharing FeSe4 tetrahedra. The twisted octahedral coordination environment of the Fe-amine complex leads to partial dimerization of Fe-Fe distances in the FeSe2 chains so that the FeSe4 polyhedra deviate strongly from the regular tetrahedral geometry. 57Fe Mössbauer spectroscopy reveals oxidation states of +3 for the Fechain atoms and +2 for the Fecomplex atoms. The close proximity of Fe atoms in the chains promotes ferromagnetic nearest neighbor interactions, as indicated by a positive Weiss constant, θ = +53.8(6) K, derived from the Curie-Weiss fitting. Magnetometry and heat capacity reveal two consecutive magnetic transitions below 10 K. DFT calculations suggest that the ordering observed at 4 K is due to antiferromagnetic intrachain interactions in the 1D-FeSe2 chains. The combination of two different ligands creates an asymmetric coordination environment that induces changes in the structure of the Fe-Se fragments. This synthetic strategy opens new ways to explore the effects of ligand field strength on the structure of both Fe-amine complexes and surrounding Fe-Se chains.

As-Se Pentagonal Linkers to Induce Chirality and Polarity in Mixed-Valent Fe-Se Tetrahedral Chains Resulting in Hidden Magnetic Ordering.

A novel mixed-valent hybrid chiral and polar compound, Fe7As3Se12(en)6(H2O), has been synthesized by a single-step solvothermal method. The crystal structure consists of 1D [Fe5Se9] chains connected via [As3Se2]-Se pentagonal linkers and charge-balancing interstitial [Fe(en)3]2+ complexes (en = ethylenediamine). Neutron powder diffraction verified that interstitial water molecules participate in the crystal packing. Magnetic polarizability of the produced compound was confirmed by X-ray magnetic circular dichroism (XMCD) spectroscopy. X-ray absorption spectroscopy (XAS) and 57Fe Mössbauer spectroscopy showed the presence of mixed-valent Fe2+/Fe3+ in the Fe-Se chains. Magnetic susceptibility measurements reveal strong antiferromagnetic nearest neighbor interactions within the chains with no apparent magnetic ordering down to 2 K. Hidden short-range magnetic ordering below 70 K was found by 57Fe Mössbauer spectroscopy, showing that a fraction of the Fe3+/Fe2+ in the chains are magnetically ordered. Nevertheless, complete magnetic ordering is not achieved even at 6 K. Analysis of XAS spectra demonstrates that the fraction of Fe3+ in the chain increases with decreasing temperature. Computational analysis points out several competing ferrimagnetic ordered models within a single chain. This competition, together with variation in the Fe oxidation state and additional weak intrachain interactions, is hypothesized to prevent long-range magnetic ordering.

Tuning Fe-Se Tetrahedral Frameworks by a Combination of [Fe(en)3]2+ Cations and Cl- Anions.

A one-dimensional (1D) chain compound [Fe(en)3]3(FeSe2)4Cl2 (en = ethylenediamine), featuring tetrahedral FeSe2 chains separated by [Fe(en)3]2+ cations and Cl- anions, has been synthesized by a low temperature solvothermal method using simple starting materials. The degree of distortion in the Fe-Se backbone is similar to previously reported compounds with isolated 1D FeSe2 chains. 57Fe Mössbauer spectroscopy reveals the mixed-valent nature of [Fe(en)3]3(FeSe2)4Cl2 with Fe3+ centers in the [FeSe2]- chains and Fe2+ centers in the [Fe(en)3]2+ complexes. SQUID magnetometry indicates that [Fe(en)3]3(FeSe2)4Cl2 is paramagnetic with a reduced average effective magnetic moment, µeff = 9.51 µB per formula unit, and a negative Weiss constant, θ = -10.9(4) K, indicating antiferromagnetic (AFM) nearest neighbor interactions within the [FeSe2]- chains. Weak antiferromagnetic coupling between chains, combined with rather strong intrachain AFM coupling, leads to spin-glass behavior at low temperatures, as indicated by a frequency shift of the peak observed at 3 K in AC magnetic measurements. A combination of [Fe(en)3]2+ and Cl- ions is also capable of stabilizing mixed-valent 2D Fe-Se puckered layers in the crystal structure of [Fe(en)3]4(Fe14Se21)Cl2, where Fe14Se21 layers have a unique topology with large open pores. Property measurements of [Fe(en)3]4(Fe14Se21)Cl2 could not be performed due to the inability to either grow large crystals or synthesize this material in single-phase form.

NsrR from Streptomyces coelicolor is a nitric oxide-sensing [4Fe-4S] cluster protein with a specialized regulatory function.

The Rrf2 family transcription factor NsrR controls expression of genes in a wide range of bacteria in response to nitric oxide (NO). The precise form of the NO-sensing module of NsrR is the subject of controversy because NsrR proteins containing either [2Fe-2S] or [4Fe-4S] clusters have been observed previously. Optical, Mössbauer, resonance Raman spectroscopies and native mass spectrometry demonstrate that Streptomyces coelicolor NsrR (ScNsrR), previously reported to contain a [2Fe-2S] cluster, can be isolated containing a [4Fe-4S] cluster. ChIP-seq experiments indicated that the ScNsrR regulon is small, consisting of only hmpA1, hmpA2, and nsrR itself. The hmpA genes encode NO-detoxifying flavohemoglobins, indicating that ScNsrR has a specialized regulatory function focused on NO detoxification and is not a global regulator like some NsrR orthologues. EMSAs and DNase I footprinting showed that the [4Fe-4S] form of ScNsrR binds specifically and tightly to an 11-bp inverted repeat sequence in the promoter regions of the identified target genes and that DNA binding is abolished following reaction with NO. Resonance Raman data were consistent with cluster coordination by three Cys residues and one oxygen-containing residue, and analysis of ScNsrR variants suggested that highly conserved Glu-85 may be the fourth ligand. Finally, we demonstrate that some low molecular weight thiols, but importantly not physiologically relevant thiols, such as cysteine and an analogue of mycothiol, bind weakly to the [4Fe-4S] cluster, and exposure of this bound form to O2 results in cluster conversion to the [2Fe-2S] form, which does not bind to DNA. These data help to account for the observation of [2Fe-2S] forms of NsrR.

Nitrosylation of Nitric-Oxide-Sensing Regulatory Proteins Containing [4Fe-4S] Clusters Gives Rise to Multiple Iron-Nitrosyl Complexes.

The reaction of protein-bound iron-sulfur (Fe-S) clusters with nitric oxide (NO) plays key roles in NO-mediated toxicity and signaling. Elucidation of the mechanism of the reaction of NO with DNA regulatory proteins that contain Fe-S clusters has been hampered by a lack of information about the nature of the iron-nitrosyl products formed. Herein, we report nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT) calculations that identify NO reaction products in WhiD and NsrR, regulatory proteins that use a [4Fe-4S] cluster to sense NO. This work reveals that nitrosylation yields multiple products structurally related to Roussin's Red Ester (RRE, [Fe2 (NO)4 (Cys)2 ]) and Roussin's Black Salt (RBS, [Fe4 (NO)7 S3 ]. In the latter case, the absence of 32 S/34 S shifts in the Fe-S region of the NRVS spectra suggest that a new species, Roussin's Black Ester (RBE), may be formed, in which one or more of the sulfide ligands is replaced by Cys thiolates.

Quasi-three-coordinate iron and cobalt terphenoxide complexes {Ar(iPr8)OM(µ-O)}2 (Ar(iPr8) = C6H-2,6-(C6H2-2,4,6-(i)Pr3)2-3,5-(i)Pr2; M = Fe or Co) with M(III)2(µ-O)2 core structures and the peroxide dimer of 2-oxepinoxy relevant to benzene oxidation.

The bis(µ-oxo) dimeric complexes {Ar(iPr8)OM(µ-O)}2 (Ar(iPr8) = C6H-2,6-(C6H2-2,4,6-(i)Pr3)2-3,5-(i)Pr2; M = Fe (1), Co (2)) were prepared by oxidation of the M(I) half-sandwich complexes {Ar(iPr8)M(η(6)-arene)} (arene = benzene or toluene). Iron species 1 was prepared by reacting {Ar(iPr8)Fe(η(6)-benzene)} with N2O or O2, and cobalt species 2 was prepared by reacting {Ar(iPr8)Co(η(6)-toluene)} with O2. Both 1 and 2 were characterized by X-ray crystallography, UV-vis spectroscopy, magnetic measurements, and, in the case of 1, Mössbauer spectroscopy. The solid-state structures of both compounds reveal unique M2(µ-O)2 (M = Fe (1), Co(2)) cores with formally three-coordinate metal ions. The Fe···Fe separation in 1 bears a resemblance to that in the Fe2(µ-O)2 diamond core proposed for the methane monooxygenase intermediate Q. The structural differences between 1 and 2 are reflected in rather differing magnetic behavior. Compound 2 is thermally unstable, and its decomposition at room temperature resulted in the oxidation of the Ar(iPr8) ligand via oxygen insertion and addition to the central aryl ring of the terphenyl ligand to produce the 5,5'-peroxy-bis[4,6-(i)Pr2-3,7-bis(2,4,6-(i)Pr3-phenyl)oxepin-2(5H)-one] (3). The structure of the oxidized terphenyl species is closely related to that of a key intermediate proposed for the oxidation of benzene.

NH4FeCl2(HCOO): synthesis, structure, and magnetism of a novel low-dimensional magnetic material.

Solvothermal synthesis was used to create a low-dimensional iron(II) chloride formate compound, NH4FeCl2(HCOO), that exhibits interesting magnetic properties. NH4FeCl2(HCOO) crystallizes in the monoclinic space group C2/c (No. 15) with a = 7.888(1) Å, b = 11.156(2) Å, c = 6.920(2) Å, and ß = 108.066(2)°. The crystal structure consists of infinite zigzag chains of distorted Fe(2+)-centered octahedra linked by µ2-Cl and syn-syn formate bridges, with interchain hydrogen bonding through NH4(+) cations holding the chains together. The unique Fe(2+) site is coordinated by four equatorial chlorides at a distance of 2.50 Å and two axial oxygens at a distance of 2.08 Å. Magnetic measurements performed on powder and oriented single-crystal samples show complex anisotropic magnetic behavior dominated by antiferromagnetic interactions (TN = 6 K) with a small ferromagnetic component in the direction of chain propagation. An anisotropic metamagnetic transition was observed in the ordered state at 2 K in an applied magnetic field of 0.85-3 T. (57)Fe Mössbauer spectroscopy reveals mixed hyperfine interactions below the ordering temperature, with strong electric field gradients and complex noncollinear arrangement of the magnetic moments.

Chemical excision of tetrahedral FeSe(2) chains from the superconductor FeSe: synthesis, crystal structure, and magnetism of Fe(3)Se(4)(en)(2).

Fragments of the superconducting FeSe layer, FeSe2 tetrahedral chains, were stabilized in the crystal structure of a new mixed-valent compound Fe3Se4(en)2 (en = ethylenediamine) synthesized from elemental Fe and Se. The FeSe2 chains are separated from each other by means of Fe(en)2 linkers. Mössbauer spectroscopy and magnetometry reveal strong magnetic interactions within the FeSe2 chains which result in antiferromagnetic ordering below 170 K. According to DFT calculations, anisotropic transport and magnetic properties are expected for Fe3Se4(en)2. This compound offers a unique way to manipulate the properties of the Fe-Se infinite fragments by varying the topology and charge of the Fe-amino linkers.

Characterization of [4Fe-4S] cluster vibrations and structure in nitrogenase Fe protein at three oxidation levels via combined NRVS, EXAFS, and DFT analyses.

Azotobacter vinelandii nitrogenase Fe protein (Av2) provides a rare opportunity to investigate a [4Fe-4S] cluster at three oxidation levels in the same protein environment. Here, we report the structural and vibrational changes of this cluster upon reduction using a combination of NRVS and EXAFS spectroscopies and DFT calculations. Key to this work is the synergy between these three techniques as each generates highly complementary information and their analytical methodologies are interdependent. Importantly, the spectroscopic samples contained no glassing agents. NRVS and DFT reveal a systematic 10-30 cm(-1) decrease in Fe-S stretching frequencies with each added electron. The "oxidized" [4Fe-4S](2+) state spectrum is consistent with and extends previous resonance Raman spectra. For the "reduced" [4Fe-4S](1+) state in Fe protein, and for any "all-ferrous" [4Fe-4S](0) cluster, these NRVS spectra are the first available vibrational data. NRVS simulations also allow estimation of the vibrational disorder for Fe-S and Fe-Fe distances, constraining the EXAFS analysis and allowing structural disorder to be estimated. For oxidized Av2, EXAFS and DFT indicate nearly equal Fe-Fe distances, while addition of one electron decreases the cluster symmetry. However, addition of the second electron to form the all-ferrous state induces significant structural change. EXAFS data recorded to k = 21 Å(-1) indicates a 1:1 ratio of Fe-Fe interactions at 2.56 Å and 2.75 Å, a result consistent with DFT. Broken symmetry (BS) DFT rationalizes the interplay between redox state and the Fe-S and Fe-Fe distances as predominantly spin-dependent behavior inherent to the [4Fe-4S] cluster and perturbed by the Av2 protein environment.

Observation of the Fe-CN and Fe-CO vibrations in the active site of [NiFe] hydrogenase by nuclear resonance vibrational spectroscopy.

Nuclear inelastic scattering of (57)Fe labeled [NiFe] hydrogenase is shown to give information on different states of the enzyme. It was thus possible to detect and assign Fe-CO and Fe-CN bending and stretching vibrations of the active site outside the spectral range of the Fe-S cluster normal modes.

Real sample temperature: a critical issue in the experiments of nuclear resonant vibrational spectroscopy on biological samples.

There are several practical and intertangled issues which make the experiments of nuclear resonant vibrational spectroscopy (NRVS) on biological samples difficult to perform. The sample temperature is one of the most important issues. In NRVS the real sample temperatures can be very different from the readings on the temperature sensors. In this study the following have been performed: (i) citing and analyzing various existing NRVS data to assess the real sample temperatures during the NRVS measurements and to understand their trends with the samples' loading conditions; (ii) designing several NRVS measurements with (Et(4)N)[FeCl(4)] to verify these trends; and (iii) proposing a new sample-loading procedure to achieve significantly lower real sample temperatures and to balance among the intertangled experimental issues in biological NRVS measurements.

Shape induced symmetry in self-assembled mesocrystals of iron oxide nanocubes.

Grazing incidence small-angle scattering and electron microscopy have been used to show for the first time that nonspherical nanoparticles can assemble into highly ordered body-centered tetragonal mesocrystals. Energy models accounting for the directionality and magnitude of the van der Waals and dipolar interactions as a function of the degree of truncation of the nanocubes illustrated the importance of the directional dipolar forces for the formation of the initial nanocube clusters and the dominance of the van der Waals multibody interactions in the dense packed arrays.

Structural properties of PbTe quantum dots revealed by high-energy x-ray diffraction.

High-energy X-ray diffraction (HE-XRD) experiments combined with an analysisbased on atomic-pair-distribution functions can be an effective tool for probing low-dimensional materials. Here, we show how such an analysis can be used to gain insightinto structural properties of PbTe nanoparticles. We interpret our HE-XRD data using anorthorhombic Pnma phase of PbTe, which is an orthorhombic distortion of the rocksalt phase.Although local crystal geometry can vary substantially with particle size at scales below 10 nm,and for very small nanoparticles the particle size itself influences X-ray diffraction patterns,our study shows that HE-XRD can provide a unique nano-characterization tool for unravelingstructural properties of nanoscale systems.

Magnetic properties of γ-Fe2O3nanoparticles in a porous SiO2shell for drug delivery.

A method is presented for synthesizing core-shell nanoparticles with a magnetic core and a porous shell suitable for drug delivery and other medical applications. The core contains multiple $\gamma$-Fe$_2$O$_3$ nanoparticles ($\sim$15~nm) enclosed in a SiO$_2$ ($\sim$100-200~nm) matrix using either methyl (denoted TMOS-$\gamma$-Fe$_2$O$_3$) or ethyl (TEOS-$\gamma$-Fe$_2$O$_3$) template groups. Low-temperature M{\"o}ssbauer spectroscopy showed that the magnetic nanoparticles have the maghemite structure, $\gamma$-Fe$_2$O$_3$, with all the vacancies in the octahedral sites. Saturation magnetization measurements revealed that the density of $\gamma$-Fe$_2$O$_3$ was greater in the TMOS-$\gamma$-Fe$_2$O$_3$ nanoparticles than TEOS-$\gamma$-Fe$_2$O$_3$ nanoparticles, presumably because of the smaller methyl group. Magnetization measurements showed that the blocking temperature is around room temperature for the TMOS-$\gamma$-Fe$_2$O$_3$ and around 250~K for the TEOS-$\gamma$-Fe$_2$O$_3$. Three dimensional topography analysis shows clearly that the magnetic nanoparticles are not only at the surface but have penetrated deep in the silica to form the core-shell structure.

Bimetallic Fe/Al system: An all-in-one solid-phase Fenton reagent for generation of hydroxyl radicals under oxic conditions.

In the classic Fenton reaction, both H2O2 and ferrous ion (Fe(II)) are required under a narrow low pH range to produce hydroxyl radicals (OH). The modified Fenton processes including heterogeneous Fenton-like reaction, photo-Fenton reaction and electro-Fenton reaction developed to overcome the drawbacks of the homogeneous Fenton reaction have recently received increasing attention. However, all the modifications of the classic Fenton reaction cannot be assembled into one system and require external supply of reagents or energy. We present here, bimetallic Fe/Al, a novel solid-phase Fenton reagent capable of in situ generation of H2O2 and Fe(II) to form OH under near neutral pH conditions without an external energy supply. Aluminum acts as an electron donor to maintain the electron supply and preserve the outer layer of iron at the zero-valence state with enhanced surface areas. The production of OH by bimetallic Fe/Al was quantified and further detected by an electron paramagnetic resonance (EPR) analysis under oxic conditions. Radical scavenging tests were performed by adding isopropanol or 1,4­benzoquinone in the system to investigate the nature of the oxidants produced during the oxidative process. Bimetallic Fe/Al system for the Fenton reaction in water involves both surface-mediated and aqueous-phase reactions. A pilot scale test using a continuous-flow column packed with Fe/Al (9.8 kg) demonstrated the capability of bimetallic Fe/Al for COD removal of acidic dye solutions. The novelty of bimetallic Fe/Al is that it is an all-in-one solid-phase Fenton reagent that can be readily applied to a wide variety of environmental applications.

Characterization of the [3Fe-4S](0/1+) cluster from the D14C variant of Pyrococcus furiosus ferredoxin via combined NRVS and DFT analyses.

The D14C variant of Pyrococcus furiosus ferredoxin provides an extraordinary framework to investigate a [3Fe-4S] cluster at two oxidation levels and compare the results to its physiologic [4Fe-4S] counterpart in the very same protein. Our spectroscopic and computational study reveals vibrational property changes related to the electronic and structural aspects of both Fe-S clusters.

Synthesis and controllable oxidation of monodisperse cobalt-doped wüstite nanoparticles and their core-shell stability and exchange-bias stabilization.

Cobalt-doped wüstite (CWT), Co0.33Fe0.67O, nanoparticles were prepared via the thermal decomposition of CoFe2-oleate complexes in organic solvents. A controllable oxidation process was then performed to obtain Co0.33Fe0.67O/CoFe2O4 core-shell structures with different core-to-shell volume ratios and exchange bias properties. The oxidized core-shell samples with a ∼4 nm CoFe2O4 shell showed good resistance to oxygen transmission. Thus, it is inferred that the cobalt ferrite shell provides a better oxidation barrier performance than magnetite in the un-doped case. The hysteresis loops of the oxidized 19 nm samples exhibited a high exchange bias field (H(E)), an enhanced coercivity field (H(C)), and a pronounced vertical shift, thus indicating the presence of a strong exchange bias coupling effect. More importantly, the onset temperature of H(E) was found to be higher than 200 K, which suggests that cobalt doping increases the Néel temperature (T(N)) of the CWT core. In general, the results show that the homogeneous dispersion of Co in iron precursors improves the stability of the final CWT nanoparticles. Moreover, the CoFe2O4 shells formed following oxidation increase the oxidation resistance of the CWT cores and enhance their anisotropy energy.

Control over connectivity and magnetism of tetrahedral FeSe2 chains through coordination Fe-amine complexes.

The synthesis and structural characterization is reported for [Fe(dien)2][FeSe2]2 and [Fe(tren)][FeSe2]2, two new mixed-valence compounds that contain infinite ∞(1)(FeSe2) tetrahedral chains separated by Fe-amine complexes. The inter- and intra-chain magnetic interactions can be controlled by changing the denticity of the amine while preserving the general structural motif.

High-Temperature Magnetism as a Probe for Structural and Compositional Uniformity in Ligand-Capped Magnetite Nanoparticles.

To investigate magnetostructural relationships in colloidal magnetite (Fe3O4) nanoparticles (NPs) at high temperature (300-900 K), we measured the temperature dependence of magnetization (M) of oleate-capped magnetite NPs ca. 20 nm in size. Magnetometry revealed an unusual irreversible high-temperature dependence of M for these NPs, with dip and loop features observed during heating-cooling cycles. Detailed characterizations of as-synthesized and annealed Fe3O4 NPs as well as reference ligand-free Fe3O4 NPs indicate that both types of features in M(T) are related to thermal decomposition of the capping ligands. The ligand decomposition upon the initial heating induces a reduction of Fe3+ to Fe2+ and the associated dip in M, leading to more structurally and compositionally uniform magnetite NPs. Having lost the protective ligands, the NPs continually sinter during subsequent heating cycles, resulting in divergent M curves featuring loops. The increase in M with sintering proceeds not only through elimination of a magnetically dead layer on the particle surface, as a result of a decrease in specific surface area with increasing size, but also through an uncommonly invoked effect resulting from a significant change in Fe3+/Fe2+ ratio with heat treatment. The interpretation of irreversible features in M(T) indicates that reversible M(T) behavior, conversely, can be expected only for ligand-free, structurally and compositionally uniform magnetite NPs, suggesting a general applicability of high-temperature M(T) measurements as an analytical method for probing the structure and composition of magnetic nanomaterials.

Development of iron-doped silicon nanoparticles as bimodal imaging agents.

We demonstrate the synthesis of water-soluble allylamine-terminated Fe-doped Si (Si(xFe)) nanoparticles as bimodal agents for optical and magnetic imaging. The preparation involves the synthesis of a single-source iron-containing precursor, Na(4)Si(4) with x% Fe (x = 1, 5, 10), and its subsequent reaction with NH(4)Br to produce hydrogen-terminated Si(xFe) nanoparticles. The hydrogen-capped nanoparticles are further terminated with allylamine via thermal hydrosilylation. Transmission electron microscopy indicates that the average particle diameter is ∼3.0 ± 1.0 nm. The Si(5Fe) nanoparticles show strong photoluminescence quantum yield in water (∼10%) with significant T(2) contrast (r(2)/r(1) value of 4.31). Electron paramagnetic resonance and Mössbauer spectroscopies indicate that iron in the nanoparticles is in the +3 oxidation state. Analysis of cytotoxicity using the resazurin assay on HepG2 liver cells indicates that the particles have minimal toxicity.