Development and Characterization of Field Structured Magnetic Composites.

Polymer composites containing ferromagnetic fillers are promising for applications relating to electrical and electronic devices. In this research, the authors modified an ultraviolet light (UV) curable prepolymer to additionally cure upon heating and validated a permanent magnet-based particle alignment system toward fabricating anisotropic magnetic composites. The developed dual-cure acrylate-based resin, reinforced with ferromagnetic fillers, was first tested for its ability to polymerize through UV and heat. Then, the magnetic alignment setup was used to orient magnetic particles in the dual-cure acrylate-based resin and a heat curable epoxy resin system in a polymer casting approach. The alignment setup was subsequently integrated with a material jetting 3D printer, and the dual-cure resin was dispensed and cured in-situ using UV, followed by thermal post-curing. The resulting magnetic composites were tested for their filler loading, microstructural morphology, alignment of the easy axis of magnetization, and degree of monomer conversion. Magnetic characterization was conducted using a vibrating sample magnetometer along the in-plane and out-of-plane directions to study anisotropic properties. This research establishes a methodology to combine magnetic field induced particle alignment along with a dual-cure resin to create anisotropic magnetic composites through polymer casting and additive manufacturing.

Tuning the magnetism of gold nanoparticles by changing the thiol coating.

Room-temperature ferromagnetic behaviour has been reported in nanoscale materials expected to be diamagnetic, including gold. However, it is yet unclear which factors (size, shape, surface coating) predominantly influence the magnitude of the magnetic response. In this work, we study the magnetic and electronic properties of similarly-sized gold nanoparticles (Au NPs) coated with four different n-alkanethiols, as well as hydroxyl- and carboxyl-functionalized alkanethiols using superconducting quantum interference device (SQUID) magnetometry and ultraviolet photoelectron spectroscopy (UPS). We find room-temperature behaviour (hysteresis in magnetization vs. field strength loops) in all samples, as well as large effective magnetic anisotropy. Importantly, we find the nanoparticles coated with polar chain end-groups (-OH and -COOH) show markedly higher magnetization; this increased magnetization correlates with a higher work function. This work establishes chemical handles to enhance magnetism in nanoscale gold particles.

Rheology-Assisted Microstructure Control for Printing Magnetic Composites-Material and Process Development.

Magnetic composites play a significant role in various electrical and electronic devices. Properties of such magnetic composites depend on the particle microstructural distribution within the polymer matrix. In this study, a methodology to manufacture magnetic composites with isotropic and anisotropic particle distribution was introduced using engineered material formulations and manufacturing methods. An in-house developed material jetting 3D printer with particle alignment capability was utilized to dispense a UV curable resin formulation to the desired computer aided design (CAD) geometry. Formulations engineered using additives enabled controlling the rheological properties and the microstructure at different manufacturing process stages. Incorporating rheological additives rendered the formulation with thixotropic properties suitable for material jetting processes. Particle alignment was accomplished using a magnetic field generated using a pair of permanent magnets. Microstructure control in printed composites was observed to depend on both the developed material formulations and the manufacturing process. The rheological behavior of filler-modified polymers was characterized using rheometry, and the formulation properties were derived using mathematical models. Experimental observations were correlated with the observed mechanical behavior changes in the polymers. It was additionally observed that higher additive content controlled particle aggregation but reduced the degree of particle alignment in polymers. Directionality analysis of optical micrographs was utilized as a tool to quantify the degree of filler orientation in printed composites. Characterization of in-plane and out-of-plane magnetic properties using a superconducting quantum interference device (SQUID) magnetometer exhibited enhanced magnetic characteristics along the direction of field structuring. Results expressed in this fundamental research serve as building blocks to construct magnetic composites through material jetting-based additive manufacturing processes.

Three Sequential Hydrolysis Products of the Ubiquitous Cu24 Isophthalate Metal-Organic Polyhedra.

Metal-organic polyhedra (MOPs) are increasingly studied as host-guest capsules, linked into networks, or incorporated into composite materials. As such, understanding the decomposition of MOP structures is of fundamental importance. The degradation of the ubiquitous copper(II) MOP Cu24[5-(hydroxy)isophthalate]24 (1) is studied in liquid water. At different intervals of water exposure, powder X-ray diffraction (PXRD) is performed and stepwise conversion of the MOP into three different coordination polymers is observed. First, the formation of a 2D coordination polymer, 2, is observed, which upon further exposure gives a 1D coordination polymer, 3, and finally a trinuclear copper(II) complex, 4. Compound 2 is characterized by PXRD owing to its transient nature, while 3 and 4 are characterized crystallographically. The final structure, 4, contains copper(II) trimers, and so its magnetic behavior is also investigated.

Bifunctional Pyrrolidin-2-one Terminated Manganese Oxide Nanoparticles for Combined Magnetic Resonance and Fluorescence Imaging.

Multimodal probes are an asset for simplified, improved medical imaging. In particular, fluorescence and magnetic resonance imaging (MRI) are sought-after combined capabilities. Here, we show that pyrrolidin-2-one-capped manganese oxide nanoparticles (MnOpyrr NPs) combine MRI with fluorescence microscopy to function as efficient bifunctional bio-nanoprobes. We employ a one-pot synthesis for ca. 10 nm MnO NPs, wherein manganese(II) 2,4-pentadionate is thermally decomposed using pyrrolidin-2-one as a solvent and capping ligand. The MnOpyrr NPs are soluble in water without any further postsynthetic modifications. The r1 relaxivity and r2 /r1 ratio indicate that these NPs are potential T1 MRI contrast agents at clinical (3 T) and ultrahigh (9.4 T) magnetic fields. Serendipitously, the as-prepared NPs are photoluminescent. The unexpected luminescence is ascribed to the modification of the pyrrolidin-2-one during the thermal treatment. MnOpyrr NPs are successfully used to enable fluorescence microscopy of HeLa cells, demonstrating bifunctional imaging capabilities. A low cytotoxic response in two distinct cell types (HeLa, HepG2) supports the suitability of MnOpyrr NPs for biological imaging applications.

One-step ligand exchange and switching from hydrophobic to water-stable hydrophilic superparamagnetic iron oxide nanoparticles by mechanochemical milling.

We describe a simple, rapid methodology for the synthesis of water-stable iron oxide nanoparticles (IONPs) compatible with a variety of aqueous buffers, based on mechanochemical milling exchange of covalently bound surface ligands on pre-fabricated oleic acid-protected IONPs. Application of milling for IONP ligand exchange eliminates steps required for transforming hydrophobic into negatively charged, water-soluble superparamagnetic IONPs.

Water oxidation catalysis: an amorphous quaternary Ba-Sr-Co-Fe oxide as a promising electrocatalyst for the oxygen-evolution reaction.

We present an amorphous quaternary Ba-Sr-Co-Fe oxide (a-BSCF) with a specific stoichiometry, readily fabricated via a photochemical decomposition method. a-BSCF demonstrates high catalytic activity towards the oxygen-evolution reaction (OER).

Synthesis and properties of cholesteric click-phospholes.

Inspired by naturally occurring helical supramolecular architectures, a series of chiral conjugated phospholes with a cholesteryl pendant have been synthesized and characterized. The photophysically and electrochemically active conjugated phosphole species can act as dopants for the formation of chiral liquid crystals. The supramolecular structures were found to be tunable by careful choice of the conjugated headgroup as well as the rigidity of the linker of the new cholesteric phospholes.

Water oxidation catalysis: electrocatalytic response to metal stoichiometry in amorphous metal oxide films containing iron, cobalt, and nickel.

Photochemical metal-organic deposition (PMOD) was used to prepare amorphous metal oxide films containing specific concentrations of iron, cobalt, and nickel to study how metal composition affects heterogeneous electrocatalytic water oxidation. Characterization of the films by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy confirmed excellent stoichiometric control of each of the 21 complex metal oxide films investigated. In studying the electrochemical oxidation of water catalyzed by the respective films, it was found that small concentrations of iron produced a significant improvement in Tafel slopes and that cobalt or nickel were critical in lowering the voltage at which catalysis commences. The best catalytic parameters of the series were obtained for the film of composition a-Fe20Ni80. An extrapolation of the electrochemical and XPS data indicates the optimal behavior of this binary film to be a manifestation of iron stabilizing nickel in a higher oxidation level. This work represents the first mechanistic study of amorphous phases of binary and ternary metal oxides for use as water oxidation catalysts, and provides the foundation for the broad exploration of other mixed-metal oxide combinations.

Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis.

Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of a-Fe(100-y-z)Co(y)Ni(z)O(x) are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers.

Dithieno[3,2-c:2',3'-e]-2,7-diketophosphepin: a unique building block for multifunctional π-conjugated materials.

A series of conjugated materials based on the new dithieno[3,2-c:2',3'-e]-2,7-diketophosphepin (DTDKP) building block have been studied for the first time. Theoretical calculations predict DTDKP to be a better electron acceptor than the well-known dithienophosphole and the nitrogen analogue, bithiopheneimide. Cyclic voltammetry studies revealed two reduction processes that support their promising electron-acceptor properties, and modification of the P center with O or gold(I) further reduced the LUMO energy to ca. -3.6 eV. Expansion of the DTDKP core with various aromatic moieties has been realized using the Huisgen alkynyl click reaction, resulting in altered optical and electrochemical properties with compounds showing a high-energy absorption band at ca. 270-290 nm and a low-energy band at ca. 390-460 nm. The acceptor character of the DTDKP core was demonstrated by a red shift following the electron-donating strength of the appended aromatic moiety. Intriguing white-light emission from just a single species with the CIE coordinates of (0.33, 0.34) was observed for some of the extended species as the result of an unexpected dual-emission behavior. The high-energy emission in the blue-to-green region and the low-energy emission in the orange-to-red region are attributed to a π* → π transition of the DTDKP core and charge transfer from the triazole moiety to DTDKP, respectively. Apart from tuning of the molecular properties, this novel building block has also been applied in a self-assembled organogel, which exhibited pronounced luminescence. Scanning electron microscopy confirmed that the gel self-assembled by forming a network of entangled 1D fibrous structures on the micrometer scale.

Magnetic, electrochemical and spectroscopic properties of iron(III) amine-bis(phenolate) halide complexes.

Eight new iron(III) amine-bis(phenolate) complexes are reported. The reaction of anhydrous FeX(3) salts (where X = Cl or Br) with the diprotonated tripodal tetradentate ligands 2-tetrahydrofurfurylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol), H(2)L1, 2-tetrahydrofurfurylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenol), H(2)L2, and 2-methoxyethylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol), H(2)L3, 2-methoxyethylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenol), H(2)L4 produces the trigonal bipyramidal iron(III) complexes, L1FeCl (1a), L1FeBr (1b), L2FeCl (2a), L2FeBr (2b), L3FeCl (3a), L3FeBr (3b), L4FeCl (4a), and L4FeBr (4b). All complexes have been characterized using electronic absorption spectroscopy, cyclic voltammetry and room temperature magnetic measurements. Variable temperature magnetic data were acquired for complexes 2b, 3a and 4b. Variable temperature Mössbauer spectra were obtained for 2b, 3a and 4b. Single crystal X-ray molecular structures have been determined for proligand H(2)L4 and complexes 1b, 2b, and 4b.

Note: Probing quadratic magneto-optical Kerr effects with a dual-beam system.

In this Note, we present a dual-beam magneto-optical Kerr effect (MOKE) magnetometer for the study of quadratic MOKE in magnetic thin films. The two beams simultaneously probe the sample, located in the middle of a quadrupole magnet, at two angles of incidence (0 degrees and 45 degrees). This combination of two systems allows one to automatically and routinely perform measurements that are sensitive to the combined longitudinal and quadratic MOKE signals (45 degrees), or the quadratic effect alone (0 degrees). Orientation-dependent and automated quantitative analyses of the quadratic effect's amplitude are also implemented. We present representative measurements on Heusler compound thin films to illustrate the newly combined capabilities of this instrument.

Magnetic frustration and spin disorder in isostructural M(mu-OH2)2[Au(CN)2]2 (M = Mn, Fe, Co) coordination polymers containing double aqua-bridged chains: SQUID and microSR studies.

A series of isostructural M(mu-OH(2))(2)[Au(CN)(2)](2) (M = Co, Fe, and Mn) coordination polymers was synthesized from the reaction of M(II) with [(n)Bu(4)N][Au(CN)(2)]. The basic structural motif for these polymers is analogous to that of previously reported Cu(II)- and Ni(II)-containing polymers and contains repeating double aqua bridges between metal centers that yield a chain structure with pendant [Au(CN)(2)](-) units. The aqueous reaction with Fe(III) yields Fe(mu-OH(2))(mu-OH)[Au(CN)(2)](2), which has a similar structure. The magnetic properties of these polymers were investigated by a combination of SQUID magnetometry and zero-field muon spin relaxation. The double aqua bridges were found to mediate ferromagnetic interactions along the chains in the Co(II)-containing polymer, whereas intrachain antiferromagnetic interactions are present in the Fe(II)-, Fe(III)-, and Mn(II)-containing polymers. Weak magnetic interchain interactions mediated through hydrogen bonds, involving the bridging water molecules and the pendant cyanide groups, are also present. In zero field, the interchain interactions yield a phase transition to a disordered spin-frozen magnetic state below 2-5 K for every polymer. However, the degree of spin disorder varies considerably, depending on the metal center.

A closer look: magnetic behavior of a three-dimensional cyanometalate coordination polymer dominated by a trace amount of nanoparticle impurity.

The structure and properties of the K{Ni[Au(CN)(2)](3)} coordination polymer, prepared as a powder at room temperature and recrystallized hydrothermally, are reported. The structure of K{Ni[Au(CN)(2)](3)} contains triply-interpenetrated Prussian Blue type pseudo-cubic arrays assembled from the alternation of octahedral Ni(II) centers and [Au(CN)(2)](-) bridging units. SQUID magnetometry studies have shown that K{Ni[Au(CN)(2)](3)} displays typical paramagnetic behavior for isolated Ni(II) centers down to 1.8 K. However, the magnetic behavior of the samples prepared under hydrothermal conditions suggests a superparamagnetic signature superimposed onto a paramagnetic background. After investigating the samples by transmission electron microscopy, it was determined that, in addition to K{Ni[Au(CN)(2)](3)}, the high-temperature (125, 135, and 165 degrees C) aqueous reaction of Ni(NO(3))(2)6 H(2)O with KAu(CN)(2) also led to the formation of nanoparticles of NiO and Au as minor side products, and that these dominated the magnetic behavior. Nanoparticles of various sizes and shapes were observed, depending on the reaction conditions. Samples containing nanoparticles were found to be superparamagnetic, exhibiting blocking temperatures of approximately 17-22 K, consistent with the behavior expected for NiO nanoparticles. These results illustrate the extreme care that must be taken when examining the physical properties of apparently analytically pure materials prepared by hydrothermal methods.

High-pressure Raman spectroscopic study of the ammonia-borane complex. Evidence for the dihydrogen bond.

The Raman spectra of the ammonia-borane complex, NH(3)BH(3), have been investigated as a function of pressure up to 40 kbar. Vibrational modes involving the NH(3) group show negative pressure dependences, supporting the existence of the dihydrogen bond, but the vibrations of the BH(3) group have a positive dependence. Two transitions were observed in the solid phase under pressure, in contrast to the temperature behavior, where a single transition occurs. Factor group splitting occurs for the degenerate vibrations, and this allows the correct assignment of the observed vibrations.