Charles J. O'Connor

An Inorganic Double Helix: Hydrothermal Synthesis, Structure, and Magnetism of Chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]·4H2O

Very complicated inorganic solids can be self-assembled from structurally simple precursors as illustrated by the hydrothermal synthesis of the vanadium phosphate, [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]�4H2O, 1, which contains chiral double helices formed from interpenetrating spirals of vanadium oxo pentamers bonded together by P5+. These double helices are in turn intertwined with each other in a manner that generates unusual tunnels and cavities that are filled with (CH3)2NH2+ and K+ cations, respectively. The unit cell contents of dark blue phosphate 1, which crystallizes in the enantiomorphic space group P43 with lattice constants a = 12.130 and c = 30.555 angstroms, are chiral; only one enantiomorph is present in a given crystal. Magnetization measurements show that 1 is paramagnetic with ten unpaired electrons per formula unit at higher temperatures and that antiferromagnetic interactions develop at lower temperatures.

Magnetic Properties of Variable-sized Fe3O4 Nanoparticles Synthesized from Non-aqueous Homogeneous Solutions of Polyols

The magnetic behaviour of well-dispersed monodisperse Fe3O4 nanoparticles with sizes varying between 6.6 and 17.8?nm prepared in a non-aqueous medium was investigated. The smaller nanocrystals exhibit superparamagnetism with the blocking temperatures increasing with the particle size, whereas the biggest particles are ferromagnetic at room temperature. The saturation magnetization values are slightly smaller than that of the bulk material, suggesting the existence of a disordered spin configuration on their surface. The thickness of the magnetically inert shell was estimated from the size variation of the magnetization at 1.9??. The dipole?dipole interactions between the particles were tuned by changing the interparticle distances, e.g. by diluting the nanopowders in a non-magnetic matrix at concentrations ranging from 0.25 to 100?wt%. As the strength of the interactions is decreased with dilution, the energy barrier is substantially lowered; this will induce a drastic decrease of both the blocking temperatures and the coercivity with decreasing concentration of the nanoparticles.

The synthesis of core–shell iron@gold nanoparticles and their characterization

Au-coated magnetic Fe nanoparticles have been successfully synthesized by partial replacement reaction in a polar aprotic solvent with about 11 nm core of Fe and about 2.5 nm shell of Au. In this work, a combination of TEM (transmission electron microscopy), XRD (X-ray powder diffractometry), EDS (energy disperse X-ray spectroscopy), SQUID (superconducting quantum interference device), TGA (thermograviometric analysis) and UV–visible absorption spectroscopy were employed to characterize the morphology, structure, composition and magnetic properties of the products. HRTEM images show clear core–shell structure with different crystal lattices from Fe and Au. SQUID magnetometry reveals that particle magnetic properties are not significantly affected by the overlayer of a moderately thick Au shell. The Au-coated particles exhibit a surface plasmon resonance peak that red-shifts from 520 to 680 nm. And all the above characterizations show that in this sample there are no iron oxides inside the particle.

Magnetic properties of a series of ferrite nanoparticles synthesized in reverse micelles

Nanoscale particles of the general formula MFe/sub 2/O/sub 4/ (M=Co, Mn, Fe) were synthesized in reverse micelles of twin-tailed anionic bis(2-ethylhexyl) sodium sulfosuccinate (AOT) in isooctane. The size of the particles was controlled by adjusting the AOT/water molar ratio. Particle sizes were confirmed using XRD and uniformity was determined by SEM. Magnetic measurements, carried out using a SQUID Susceptometer, indicated superparamagnetic behavior. FC and ZFC demagnetization experiments indicate blocking temperatures of 46 K, 30 K, and 7 K for for MFe/sub 2/O/sub 4/ M=Co, Mn, Fe respectively. Below blocking temperatures, the nanoparticles demonstrate hysteresis with coercivities of H/sub c/=6000G, 3800G, and 500G for the Co, Mn, and Fe ferrites.

Molybdophosphonate clusters as building blocks in the oxomolybdate-organodiphosphonate/cobalt(II)-organoimine system: structural influences of secondary metal coordination preferences and diphosphonate tether lengths.

Hydrothermal conditions have been used in the preparation of a series of organic-inorganic hybrid materials of the cobalt-molybdophosphonate family. The reactions of MoO(3), cobalt(II) acetate or cobalt(II) acetylacetonate, tetra-2-pyridylpyrazine (tpyprz), and organodiphosphonic acids H(2)O(3)P(CH(2))nPO(3)H(2) (n = 1-5 and 9) of varying tether lengths yielded compounds of the general type {Co(2)(tpyprz)(H(2)O)(m)}4+/MoxOy{O(3)P(CH(2))(n)PO(3)}z. The recurring theme of the structural chemistry is the incorporation of {Mo(5)O(15)(O(3)PR)(2)}(4-) clusters as molecular building blocks observed in the structures of nine phases (compounds 2-9 and 11). The structural consequences of variations in reaction conditions are most apparent in the series with propylene diphosphonate, where four unique structures 4-7 are observed, including two distinct three-dimensional architectures for compounds 5 and 6 whose formulations differ only in the number of water molecules of crystallization. With pentyldiphosphonate, a second phase 10 is obtained which exhibits a unique cluster building block, the hexamolybdate [Mo(6)O(18){O(3)P(CH(2))(5)PO(3)}](4-). In the case of methylenediphosphonic acid, a third structural motif, the trinuclear {(Mo(3)O(8))(O(3)PCH(2)PO(3))}2- subunit, is observed in compound 1. The structural chemistry of compounds 1-11 of this study is quite distinct from that of the {Ni(2)(tpyprz)(H(2)O)(m)}(4+)/Mo(x)O(y){O(3)P(CH(2))(n)PO(3)}z family, as well as that of the copper-based family. The structural diversity of this general class of materials reflects the coordination preferences of the M(II) sites, the extent of aqua ligation to the M(II) sites, the participation of both phosphate oxygen atoms and molybdate oxo-groups in linking to the M(II) sites, and the variability in the number of attachment sites at the molybdophosphonate clusters. Since the charge densities at the peripheral oxygen atoms of the clusters are quite uniform, the attachment of {M(2)(tpyprz)}(4+) subunits to the molybdophosphonates appears to be largely determined by steric, coulombic, and packing factors, as shown by extensive density functional theory calculations.

Water-Dispersible Iron Oxide Magnetic Nanoparticles with Versatile Surface Functionalities

We report a simple one-pot strategy to prepare surface-function-alized, water-dispersible iron oxide nanoparticles. Small organic molecules that have desired functional groups such as amines, carboxylics, and thiols are chosen as capping agents and are injected into the reaction medium at the end of the synthesis. A diversity of functionalities are effectively introduced onto the surface of the nanoparticles with a minimal consumption of solvents and chemical resources by simply switching the capping ligand to form the ligand shell. The resulting nanocrystals are quasi-spherical and narrowly size-distributed. Energy-dispersive X-ray analysis and Fourier transform infrared spectroscopy studies suggest a successful surface modification of iron oxide nanoparticles with selected functionalities. The colloidal stabilities are characterized by dynamic light scattering and zeta potential measurements. The results imply that functionalized nanoparticles are very stable and mostly present as individual units in buffer solutions. The pedant functional groups of the capping ligand molecules are very reactive, and their availabilities are investigated by covalently linking fluorescent dyes to the nanoparticles through the cross-linking of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. The quenched quantum yield and shortened lifetime of the dyes strongly indicate a direct bonding between the functional group of the nanoparticles and the fluorescent molecules.

Formation of ordered arrays of gold nanoparticles from CTAB reverse micelles

In this presentation, a reverse micelle technique was described to create colloid gold nanoparticles and their self-organization into superlattices. Gold nanoparticles were prepared by the reduction of HAuCL4 in CTAB/octane + 1-butanol/H2O reverse micelle system using NaBH4 as reducing agent. Dodecanethiol (C12H25SH) was used to passivate the gold nanoparticles immediately after formation of the gold colloid. After re-dispersing in toluene under ultrasonication, a supernatant containing nearly monodispersed dodecanethiol-capped gold nanoparticles was obtained. Self-organization of the gold nanoparticles into 1D, 2D and 3D superlattices was observed on the carbon-coated copper grid by TEM. UV-vis absorption spectra were also used to characterize the gold colloids with and without dodecanethiol capping

Magnetic and luminescence characteristics of dinuclear complexes of lanthanides and a phenolic schiff base macrocyclic ligand

Abstract The magnetic and luminescence characteristics of trimorphic homodinuclear macrocyclic complexes of lanthanides and a 2:2 phenolate Schiffs base L, derived from 2,6-diformyl- p -cresol and triethylenetetramine were determined. The complexes of Pr 3+ exhibit non-Curie-Weiss temperature dependent magnetic susceptibilities for which satisfactory fits to an axial relationship depends on crystal field splitting and a weak binuclear Pr 3+ Pr 3+ antiferromagnetic interaction. The exchange interaction parameters are z J ′ = −2.2, −4.4 and −7.0 cm −1 for ‘off-white’ Pr 2 L(NO 3 ) 4 ·2H 2 O, ‘yellow’ Pr 2 L(NO 3 ) 4 , and ‘orange’ Pr 2 L(NO 3 ) 2 (OH) 2 , respectively. In contrast, magnetic susceptibilities of the Ln 2 L(NO 3 ) 3 (OH) complexes (Ln = Dy, Ho) follow Curie-Weiss behavior over the entire temperature range (6 K to 300 K). The complexes of closed shell ions La 3+ , Lu 3+ , Y 3+ and those of the half filled shell ion Gd 3+ exhibit a strong ligand fluorescence in the 450 nm to 650 nm range with decay times at 77 K of 5–8 ns for Ln≠Gd or 2–4 ns for Ln = Gd. The complexes of Gd 3+ also exhibit a phosphorescence at 600 nm (decay time ∼ 200 μs). The complexes containing Ce 3+ , Eu 3+ , Tb 3+ and Er 3+ show very weak ligand luminescence indicative of effective quenching processes. Sensitized emission from the lanthanide ion is observed only with the Eu 3+ complexes ( 5 D o → 7 F j transitions). The emission lifetimes are on the order of 250 μs in the pure Eu 3+ complexes. The emission decay curves from dilute samples of Eu 3+ in ‘off-white’ La 2 L(NO 3 ) 4 n H 2 O show a noticeable rise time as well as a biphasic decay (fast component ∼ 400 μs; slow component ∼ 2500 μs). The luminescing states of L and Eu 3+ have a common excitation spectrum which is similar to the electronic absorption spectrum of L indicating that ligand-to-metal ion energy transfer processes are dominant. Overall the result if this study suggest that the spectral properties of the complexes are determined by the coordination mode of the lanthanide ions to the Schiff base portion of macrocyclic ligand.

Effects of shell thickness on blocking temperature of nanocomposites of metal particles with gold shells

Nanoscale iron particles were synthesized in reverse micelles created from aqueous reactants, octane, n-butanol, and cetyltrimethylammonium bromide (CTAB). Using reverse micelles as nano-reactors allows for the sequential synthesis of core-shell nanoparticles. Iron nanoparticles were synthesized and coated with gold. A series of particles with varying gold shell thickness were synthesized to investigate the effect of shell thickness on the magnetic properties of the iron core. Particle sizes were confirmed using XRD and particle uniformity was determined by TEM. Magnetic measurement carried out using a SQUID susceptometer indicated superparamagnetic behavior.

Construction of metal-organic oxides from molybdophosphonate clusters and copper-bipyrimidine building blocks.

A series of organic-inorganic hybrid materials of the copper(II)-molybdophosphonate family have been prepared using conventional hydrothermal conditions. The reactions of MoO(3), copper(II) acetate, bipyrimidine (bpyr), a phosphonic acid, and water at temperatures below 160 degrees C and in the presence of a mineralizer such as acetic acid or HF provided crystalline samples of materials of the general class {Cu(2)(bpyr)}(4+)/Mo(x)O(y)-phosphonate. The recurrent themes of the structures are the presence of the binuclear {Cu(2)(bpyr)}(4+) and pentanuclear {Mo(5)O(15)(O(3)PR)(2)}(4-) building blocks. For the alkylphosphonate-containing materials, [{Cu(2)(bpyr)(2)}Mo(5)O(15)(O(3)PCH(3))(2)].2.5H(2)O (1.2.5H(2)O) is two-dimensional and exhibits {Cu(bpyr)}(n)(2n+) chains, while [{Cu(2)(bpyr)(H(2)O)}Mo(5)O(15)(O(3)PCH(2)CH(3))(2)] (2) is three-dimensional. The diphosphonate series of materials {{Cu(2)(bpyr)}(4+)[Mo(5)O(15){O(3)P(CH(2))(n)PO(3)}](4-) with n = 2-6 (4, 5, 7-9) in all cases contain the characteristic [Mo(5)O(15){O(3)P(CH(2))(n)PO(3)}](n)(2n+) chains, linked through {Cu(2)(bpyr)}(4+) rods into three-dimensional frameworks. When n = 1, the three-dimensional phase [{Cu(2)(bpyr)}MoO(2)(HO(3)PCH(2)PO(3))(2)].2H(2)O (3.2H(2)O) is obtained, the exclusive example of a structure constructed from isolated {MoO(6)} polyhedra rather than pentamolybdate clusters. The Ni(II)-containing phase [{Ni(2)(bpyr)(H(2)O)(4)}Mo(5)O(15){O(3)P(CH(2))(3)PO(3)}].9H(2)O (6.9H(2)O) was also prepared and compared to the structure of the Cu(II) analogue, [{Cu(2)(bpyr)(H(2)O)(4)}Mo(5)O(15){O(3)P(CH(2))(3)PO(3)}].3H(2)O (5.3H(2)O). Magnetic susceptibility studies of the compounds revealed that the magnetic behavior was consistent in all cases with antiferromagnetically coupled dimers. However, the magnitude of the exchange coupling was clearly dependent on the orientation of the M(II) mean equatorial or basal planes relative to the bipyrimidine plane. Thus, when the metal and bipyrimidine planes are nearly coplanar, the J values are in the -77 to -87 cm(-1) range, while J values of -2 to -5 cm(-1) are observed for the compounds with out-of-plane orientations.