Unpaired Electron Density Research Articles

Interplay of stereo-electronic, environmental, and dynamical effects in determining the EPR parameters of aromatic spin-probes: INDCO as a test case

An integrated computational strategy for the evaluation of reliable structures and magnetic properties of spin probes and spin labels has been extended to aromatic species. From an electronic point of view, delocalization of the unpaired electron density over aromatic moieties reduces significantly the computed nitrogen isotropic hyperfine coupling constant (A(N)) with respect to values characteristic of aliphatic nitroxides. Solvent effects in not too high polarity media are quite small, but not negligible. At this stage computed A(N) are lower than their experimental counterparts by more than 1 G. Inclusion of vibrational averaging effects by molecular dynamics simulations with a new reliable force field restores full agreement with experiment pointing out the limits of static approaches irrespective of the sophistication of the electronic quantum mechanical method. The generality and computational effectiveness of the proposed integrated approach paves the route toward a reliable analysis of the interplay of stereo-electronic, environmental, and dynamical effects in tuning the properties of large flexible magnetic systems of biological and technological interest.

The Fourier transform microwave spectrum of the arsenic dicarbide radical (CCAs: X̃Π1∕22) and its C13 isotopologues

The pure rotational spectrum of the CCAs radical in its ground electronic and spin state, X (2)Pi(12), has been measured using Fourier transform microwave techniques in the frequency range of 12-40 GHz. This species was created in a supersonic expansion from a reaction mixture of AsCl(3) and C(2)H(2) or CH(4) diluted in high pressure argon, using a pulsed nozzle containing a dc discharge source. Three rotational transitions were measured for the main isotopologue, (12)C(12)CAs, in the Omega=12 ladder; both lambda-doubling and arsenic (I=32) hyperfine interactions were observed in these spectra. In addition, two to four rotational transitions were recorded for the (13)C(13)CAs, (13)C(12)CAs, and (12)C(13)CAs species. In these three isotopologues, hyperfine splittings were also resolved arising from the (13)C nuclei (I=12), creating complex spectral patterns. The CCAs spectra were analyzed with a case (a) Hamiltonian, and effective rotational, lambda-doubling, and arsenic and carbon-13 hyperfine constants were determined for the Omega=12 ladder. From the effective rotational constants of the four isotopologues, an r(m) ((1)) structure has been derived with r(C-C)=1.287 A and r(C-As)=1.745 A. These bond lengths indicate that the predominant structure for arsenic dicarbide is C=C=As, with some contributing C[Triple Bond]C and C[Triple Bond]As triple bond characters. The hyperfine constants established in this work indicate that about 23 of the unpaired electron density lies on the arsenic atom, with the remaining percentage on the terminal carbon. The value of the arsenic quadrupole coupling constant (eqQ=-202 MHz) suggests that the As-C bond has a mixture of covalent and ionic characters, consistent with theoretical predictions that both pi backbonding and electron transfer play a role in creating a linear, as opposed to a cyclic, structure for certain heteroatom dicarbides.

Partial cross-sections of hydrated hydronium reduction

Cross-sections of the hydrogen atom formation upon the electron capture by positively charged hydronium–water clusters in gas phase are found with the use of the Breit–Wigner approximation. Calculations are based on the data of quantum chemical studies of H3O+(H2O)n and H3O(H2O)n clusters, including the estimated average density of high-lying states of the radicals, the determined character of the unpaired electron density distribution, and the constructed dependence of the electron–cation interaction energy on the number of water molecules. Lifetimes of the radicals before the dissociation are taken from the classical nonempirical molecular dynamics runs.

Exploring Photoreactions between Polyazaaromatic Ru(II) Complexes and Biomolecules by Chemically Induced Dynamic Nuclear Polarization Measurements

Steady-state (1)H photo-chemically induced dynamic nuclear polarization (CIDNP) experiments were conducted at 14.1 T on deoxygenated (buffered pH 7) aqueous solutions of [Ru(phen)(3)](2+), [Ru(tap)(2)(phen)](2+), and [Ru(tap)(3)](2+) (tap = 1,4,5,8-tetraazaphenanthrene; phen = 1,10-phenanthroline) in the presence of guanosine-5'-monophosphate or N-acetyltyrosine. For the first time, CIDNP arising from photo-oxidation by polyazaaromatic Ru(II) complexes is reported. In agreement with the occurrence of a photo-electron-transfer process, photo-CIDNP effects are observed with [Ru(tap)(3)](2+) and [Ru(tap)(2)(phen)](2+) but not with [Ru(phen)(3)](2+). With [Ru(tap)(2)(phen)](2+), no significant photo-CIDNP is observed for the (1)H nuclei of the phen ligand, consistent with the fact that the metal-to-ligand charge-transfer triplet excited states responsible for the photo-oxidation involve a tap ligand. Successive experiments with [Ru(tap)(3)](2+) highlight the accumulation of long-lived radical species in solution that cause (1)H NMR signal broadening and photo-CIDNP extinction. The (1)H photo-CIDNP observed for the biomolecules is rather weak, less than about 30% of the equilibrium magnetization. However, up to 60% polarization enhancement is observed for H-2 and H-7 of the tap ligands, which indicates high unpaired electron density in the vicinity of these atoms in the transient radical pair. This is consistent with the structure of known photoadducts formed, for instance, between the metallic compounds and the guanine base of mono- and polynucleotides. Indeed, in these adducts the covalent bond involves carbon C-2 or C-7 of a tap ligand. The occurrence of photo-CIDNP with polyazaaromatic Ru(II) complexes opens new perspectives for the study of this type of compound.

Topology of the Effectively Paired and Unpaired Electron Densities for Complex Bonding Patterns: The Three-Center Two-Electron Bonding Case.

Our previously reported local formalism of the electron density decomposition into effectively paired and unpaired densities is applied to electron deficient molecular systems possessing complex bonding patterns. It is shown that the unpaired density is not only near the nuclear positions, like in classical bonds, but also spills out over the bonding regions, to compensate the electron deficiency. Topological information obtained from the effectively unpaired density, which may not be directly observed from the total density, allows us to establish a procedure to detect complex interactions. This study is complemented with results arising from nonlocal formalism of topological population analyses. The conclusions from both formalisms are in complete agreement and permit to interpret the well-known structural information from Lipscomb styx numbers going beyond it in cases where the electronic description becomes ambiguous, pointing out the subtle information contained in the unpaired density. Numerical results for three-center two-electron bondings in the boranes B2H6, B4H10, B5H9, and B5H11 are reported.

Fourier transform microwave spectroscopy of CH2CFO

Rotational spectra of the CH(2)CFO radical in the (2)A(") ground state with resolved fine and hyperfine structures have been observed for the first time by Fourier transform microwave spectroscopy. Rotational transitions are analyzed using the ordinary rigid asymmetric top Hamiltonian for doublet species with three nuclear spins. Seventeen molecular constants including the fine and hyperfine coupling constants have been determined. The CH(2)CFO radical is confirmed to be a planer molecule in the ground electronic state since it has a small positive inertial defect. From the hyperfine coupling constants of protons, the unpaired electron density on the CH(2) carbon atom is estimated to be about 85%. Thus, the formylmethyl-type resonance form (CH(2)CF=O) is a dominant structure in the ground electronic state, and fluorine substitution has negligible effect on the C-C-O pi conjugate system.

The Production and Characterisation of Novel Conducting Redox‐Active Oligomeric Thin Films From Electrooxidised Indolo[3,2,1‐jk]carbazole

Indolo[3,2,1-jk]carbazole (IC) has been synthesised on a gram scale by flash vacuum pyrolysis. In contrast to a previous suggestion, IC is planar and it is also highly fluorescent, with a solution quantum yield of 0.41. Electro-oxidation of IC at a rotating disc electrode resulted in the passage of steady-state currents and the reproducible formation of conducting, redox-active films with constituent species that are also highly fluorescent. Unusually for coupled electroactive N-heterocyclic systems, electrochemical and spectroscopic characterisation revealed the film to consist exclusively of three redox-active (2,2', 5,5' and 2,5' coupled) IC dimers with no polymeric products. Calculations showed this coupling pattern to be consistent with IC radical-cation coupling through the accessible sites of highest unpaired electron density. The unusual combination of a high dimer second oxidation potential and a negligible dimer-dimer coupling rate explains the lack of further coupling. The identities of the dimeric species were confirmed by independent syntheses involving the Suzuki-Miyaura coupling of IC boronic acids as the key step. Electro-oxidation of the IC system therefore offers a ready route to novel conducting, redox-active molecular films and their redox-active, luminescent dimer constituents.

Impact of Reduction on the Properties of Metal Bisdithiolenes: Multinuclear Solid-State NMR and Structural Studies on Pt(tfd)2 and Its Reduced Forms

Transition-metal dithiolene complexes have interesting structures and fascinating redox properties, making them promising candidates for a number of applications, including superconductors, photonic devices, chemical sensors, and catalysts. However, not enough is known about the molecular electronic origins of these properties. Multinuclear solid-state NMR spectroscopy and first-principles calculations are used to examine the molecular and electronic structures of the redox series [Pt(tfd)(2)](z-) (tfd = S(2)C(2)(CF(3))(2); z = 0, 1, 2; the anionic species have [NEt(4)](+) countercations). Single-crystal X-ray structures for the neutral (z = 0) and the fully reduced forms (z = 2) were obtained. The two species have very similar structures but differ slightly in their intraligand bond lengths. (19)F-(195)Pt CP/CPMG and (195)Pt magic-angle spinning (MAS) NMR experiments are used to probe the diamagnetic (z = 0, 2) species, revealing large platinum chemical shielding anisotropies (CSA) with distinct CS tensor properties, despite the very similar structural features of these species. Density functional theory (DFT) calculations are used to rationalize the large platinum CSAs and CS tensor orientations of the diamagnetic species using molecular orbital (MO) analysis, and are used to explain their distinct molecular electronic structures in the context of the NMR data. The paramagnetic species (z = 1) is examined using both EPR spectroscopy and (13)C and (19)F MAS NMR spectroscopy. Platinum g-tensor components were determined by using solid-state EPR experiments. The unpaired electron spin densities at (13)C and (19)F nuclei were measured by employing variable-temperature (13)C and (19)F NMR experiments. DFT and ab initio calculations are able to qualitatively reproduce the experimentally measured g-tensor components and spin densities. The combination of experimental and theoretical data confirm localization of unpaired electron density in the pi-system of the dithiolene rings.

Rate constants of atomic hydrogen formation in H3O+(H2O) n + e → H + (H2O) n gas-phase processes

Using the Maxwellian electron velocity distribution and the Breit-Wigner approximation of the reaction cross section, the kinetic parameters of the hydrogen atom formation upon the electron capture by positively charged hydronium-water clusters are estimated. Calculations of the cross sections and rate constants are based on the data of quantum chemical studies of H3O+(H2O) n and H3O(H2O) n clusters, particularly on the detailed analysis of the spacing of high-lying states of the radicals and the character of the unpaired electron density distribution, as well as on the general trend in the electron affinity change of the cations depending on the number of water molecules. The lifetimes of the radicals before the dissociation are taken from the classical nonempirical molecular dynamics runs. The results are compared to available experimental data.

Interaction of [rad]CH2OH with silver cation in Ag–A/CH3OH zeolite: A DFT study

Density functional theory (DFT) has been applied to model the structure of (AgCH2OH/A)+ complexes previously experimentally characterized by electron paramagnetic resonance (EPR) in zeolite matrices. The magnetic parameters of (AgCH2OH/A)+ were found to depend on the local structure of the zeolite represented by clusters referred to as 3T and 6T, and also on the applied computational method. A spin distribution analysis confirms the one-electron silver–carbon bonding, showing delocalization of an unpaired electron density distributed between the sliver and carbon atoms along the one-electron silver–carbon bond. The results are of relevance for a deeper understanding of the electronic and catalytic properties of zeolites containing silver atoms and clusters.

Effects of UV Irradiation on ESR and Optical Properties of Cu(II) Ions in Organic Solid Solutions Containing CuCl at 77 K

The effect of uv irradiation on the solid solutions of MTHF and EtOH containing CuCl with HCl has been in- vestigated. The axial ESR spectra observed before uv irradiation at 73 K for these solutions indicate that Cu(II) ions exist in such a way that the unpaired electron density locates on 3d 9 orbital in the coordination structure associated with the ligand molecules. The new ESR signals observed after uv irradiation is inferred to Cu(II) ions of a transformed ligand structure that is formed via an exciplex adiabatically. We infer that the new species induced by uv irradiation forms strong covalent bonds between Cu(II) ions and the ligand. The formation of the exciplex has also been evidenced by the absorption and emission properties for the same solutions at 77 K. Three types of emissive exciplexes have been pro- posed.

Near-infrared Fourier-transform and millimeterwave spectra of the BiS radical

This paper reports the 6400–7400 cm −1 Fourier-transform (FT) near-infrared (NIR) emission spectrum of the BiS X 2 2Π 3/2 → X 1 2Π 1/2 fine structure bands as well as the millimeterwave rotational spectrum of the X 1 2Π 1/2 state. For the FTNIR observations, BiS was produced by reaction of bismuth with sulfur vapor and excited by energy transfer from metastable oxygen, O 2( a 1Δ g ), in a fast-flow system. As was the case for BiO [O. Shestakov, R. Breidohr, H. Demes, K.D. Setzer, E.H. Fink, J. Mol. Spectrosc. 190 (1998) 28–77], the 0.5 cm −1resolution spectrum revealed a number of strong bands in the Δv = 0 and ±1 sequences which showed perturbed band spacings, band shapes, and intensities due to avoided crossing of the X 2 2Π 3/2 and A 1 4Π 3/2 potential curves for v ′ ⩾ 4 of X 2 2Π 3/2. The millimeterwave rotational spectrum of BiS in its X 1 2Π 1/2 state was observed when BiS was produced in a high-temperature oven by a discharge in a mixture of Bi vapor and CS 2. The signal to noise ratio was markedly improved by using a White-type multipath cell. Ninety seven features from J′ = 23.5 to J′ = 41.5 were measured between 150 and 300 GHz. Analysis of the 0.5 cm −1 resolution FT spectrum yielded the fine structure splitting and vibrational constants of the states. A simultaneous analysis of millimeterwave and a 0.005 cm −1 FT spectrum of the 0-0 band of the NIR system was carried out to give precise rotational, fine, and hyperfine constants for the X 1 2Π 1/2 and X 2 2Π 3/2 states. The results are consistent with those reported earlier for BiO and indicate only a slight decrease in the unpaired electron density in the 6p(π ∗) orbital on the Bi atom.

Explanation of atomic displacement around lattice vacancies in diamond based on electron delocalization

The relationship between unpaired electron delocalization and nearest-neighbor atomic relaxations in the vacancies of diamond has been determined in order to understand the microscopic reason behind the neighboring atomic relaxation. The Density Functional Theory (DFT) cluster method is applied to calculate the single-electron wavefunction of the vacancy in different charge states. Depending on the charge and spin state of the vacancies, at outward relaxations, 84-90% of the unpaired electron densities are localized on the first neighboring atoms. The calculated spin localizations on the first neighboring atoms in the ground state of the negatively charged vacancy and in the spin quintet excited state of the neutral vacancy are in good agreement with Electron Paramagnetic Resonance (EPR) measurements. The calculated spin localization of the positively charged vacancy contrasts with the tentative assignment of the NIRIM-3 EPR signal to this center in (p-type) semiconductor diamond. The sign of the lattice relaxation in the diamond vacancy is explained based on the effect of electron delocalization on nearest-neighbor ion-ion screening, and also its effect on the bond length of neighboring atoms.

Where Does the Electron Go? Electron Distribution and Reactivity of Peptide Cation Radicals Formed by Electron Transfer in the Gas phase

We report the first detailed analysis at correlated levels of ab initio theory of experimentally studied peptide cations undergoing charge reduction by collisional electron transfer and competitive dissociations by loss of H atoms, ammonia, and N-C alpha bond cleavage in the gas phase. Doubly protonated Gly-Lys, (GK + 2H) (2+), and Lys-Lys, (KK + 2H) (2+), are each calculated to exist as two major conformers in the gas phase. Electron transfer to conformers with an extended lysine chain triggers highly exothermic dissociation by loss of ammonia from the Gly residue, which occurs from the ground ( X ) electronic state of the cation radical. Loss of Lys ammonium H atoms is predicted to occur from the first excited ( A ) state of the charge-reduced ions. The X and A states are nearly degenerate and show extensive delocalization of unpaired electron density over spatially remote groups. This delocalization indicates that the captured electron cannot be assigned to reduce a particular charged group in the peptide cation and that superposition of remote local Rydberg-like orbitals plays a critical role in affecting the cation-radical reactivity. Electron attachment to ion conformers with carboxyl-solvated Lys ammonium groups results in spontaneous isomerization by proton-coupled electron transfer to the carboxyl group forming dihydroxymethyl radical intermediates. This directs the peptide dissociation toward NC alpha bond cleavage that can proceed by multiple mechanisms involving reversible proton migrations in the reactants or ion-molecule complexes. The experimentally observed formations of Lys z (+*) fragments from (GK + 2H) (2+) and Lys c (+) fragments from (KK + 2H) (2+) correlate with the product thermochemistry but are independent of charge distribution in the transition states for NC alpha bond cleavage. This emphasizes the role of ion-molecule complexes in affecting the charge distribution between backbone fragments produced upon electron transfer or capture.

Nanoemulsion drug delivery by ketene based polyester synthesized using electron rich carbon/silica composite surface

A new carrier matrix for nanoemulsion drug delivery was synthesized from glycine as the raw material, using mesoporous/microporous electron rich carbon–silica composite surface (MAC 800). MAC 800 was prepared from rice husk in two-stage carbonization. The surface area, pore volume, and pore size distribution of MAC 800 were measured, using nitrogen adsorption isotherms at 77 K. The unpaired electron density of MAC 800 was measured in electron spin resonance spectroscopy (ESR), using TEMPOL (4-hydroxy-2,2,6,6-tetramethyl piperidine-1-oxyl) as the reference spin probe. Glycine was converted into ketene at the surface of MAC 800, which further underwent radical polymerization to form a low molecular weight ketene polymer (LMKP) of ester structure. The structure and the properties of LMKP were confirmed through 13C, 1H and DEPT nuclear magnetic resonance (NMR) spectroscopy, attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and size exclusion chromatography (SEC). The two hydrophilic drugs namely ciprofloxacin hydrochloride (CPH) and gentamicin sulphate (GS) were chosen for the nanoemulsion preparation and characterization. They were characterized for morphology, interaction of drugs with the polymer and their crystallinity, using HR-TEM, DSC and XRD, respectively. The encapsulation efficiency of the LMKP towards the drugs ciprofloxacin hydrochloride and gentamicin sulphate were 26% and 12%, respectively. The dissolution studies of the nanoemulsion were carried out for the pH 6.5, 7.4 and 8.0. The cytocompatibility studies were done for LMKP as well as nanoemulsion using Hep2 epithelial cells.

Electronic Properties of Charge-Tagged Peptides upon Electron Capture

We report a computational study of Ala-Lys (AK) and Lys-Ala (KA) dipeptide ions furnished with fixed-charged pyridinium groups that were attached by amide linkers to the N-terminal amino groups. Cation-radicals from one-electron reduction of the doubly charged AK and KA peptide conjugates showed various extents of unpaired electron density being delocalized between the pyridine and peptide moieties. The delocalization depended on the local recombination energies (RE(loc)) of the charged groups. The RE(loc) of the pyridine moieties were modified by introducing electron-donating substituents (CH(3), OCH(3), and N(CH(3))(2)). The RE(loc) of the peptide moieties were found to depend on the peptide conformation and internal solvation of the Lys ammonium groups. Substantial electron delocalization was found for combinations of pyridine substituents and peptide conformers with closely matched RE(loc), such as 4-dimethylamino-pyridine and internally solvated Lys ammonium or unsubstituted pyridine and free (unsolvated) Lys ammonium. The dissociation (DeltaH(diss)) and transition state energies (E(TS)) for the loss of the pyridine ring from the conjugates were found to be DeltaH(diss) = 34-36 kJ mol(-1) and E(TS) = 67-69 kJ mol(-1) for the unsubstituted pyridine moieties, but did not depend much on the peptide sequence.

Electron rich porous carbon/silica matrix from rice husk and its characterization

Free electron rich porous carbon/silica matrix (ECS800) was prepared from rice husk by carbonization at 400 °C and activation by phosphoric acid (H3PO4) at 800 °C. The ratio of H3PO4 to pre-carbonized carbon was fixed at 2.3. The surface area, pore volume, and pore size distribution of ECS800 was measured, using nitrogen adsorption isotherms at 77 K. The unpaired electron density of ECS800 was measured in electron spin resonance spectroscopy, using 4-hydroxy 2,2,6,6-tetramethyl piperidine-1-oxyl as the reference spin probe. ECS800 was further characterized, using X-ray diffraction, scanning electron microscope, Fourier transform infrared spectroscope, and 29Si-nuclear magnetic resonance spectroscope to study crystallization, surface morphology, functional group and different types of silicon species.

A Proximal Bisnitroxide Initiator: Studies in Low-Temperature Nitroxide-Mediated Polymerizations.

Nitroxide-mediated "living" radical polymerization with bisalkoxyamine 2,5,5,8,8,11-hexamethyl-4,9-(1-phenylethoxy)-3,10-diphenyl-4,9-diazadodecane produces polymers of controlled length and narrow molecular weight distributions at temperatures ranging from 70 to 110 °C. Polymerizations were run successfully with styrene (St), tert-butyl acrylate (tBA), and dimethylacrylamide (DMA). EPR measurements of the homolysis of this bisalkoxyamine and monoalkoxyamine 2,2,5-trimethyl-3-(1-phenylethoxy)-4-phenyl-3-azahexane at temperatures ranging from 85 to 105 °C give rate constants for the bisalkoxyamine that are approximately twice as large as those for the monoalkoxyamine. (1)H NMR investigations of the decomposition of both alkoxyamines at 125 °C show enhanced decomposition for the bisalkoxyamine. EPR decomposition studies at 120 °C on the corresponding bis- and mononitroxides 2,5,5,8,8,11-hexamethyl-3,10-diphenyl-4,9-diazadodecane-4,9-bisnitroxide and 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide also show accelerated bisnitroxide decomposition. Low-temperature EPR studies of the bisnitroxide reveal an unusually strong radical-radical interaction, suggesting enhanced stabilization of the intermediate mononitroxide formed during polymerization by interaction with the proximal N-alkoxyamine. The transient mononitroxide is postulated to be stabilized by delocalization of the unpaired electron density over five atoms.

Coordination structures of lithium-methylamine clusters from infrared spectroscopy and ab initio calculations

Spectra of clusters formed between lithium atoms and methylamine molecules are reported for the first time. Mass-selective infrared spectra of Li(NH(2)CH(3))(n) have been recorded in both the N-H and C-H stretching fundamental regions. The infrared spectra are broadly in agreement with ab initio predictions, showing redshifted N-H stretching bands relative to free methylamine and a strong enhancement of the N-H stretching fundamentals relative to the C-H stretching fundamentals. The ab initio calculations suggest that, for n=3, the methylamine molecules bunch together on one side of the lithium atom to minimize repulsive interactions with the unpaired electron density. The addition of a fourth methylamine molecule results in closure of the inner solvation shell and, thus, Li(NH(2)CH(3))(5) is forced to adopt a two-shell coordination structure. This is consistent with neutron diffraction studies of concentrated lithium/methylamine solutions, which also suggest that the first solvation shell around the lithium atom can contain a maximum of four methylamine molecules.

Synthesis, Structure, and Unexpected Magnetic Properties of La3Re2O10

The compound La(3)Re(2)O(10) has been synthesized by solid-state reaction and characterized by powder neutron diffraction, SQUID magnetometry, and heat capacity measurements. Its structure consists of isolated [Re(2)O(10)](9-) dimer units of two edge-shared ReO(6) octahedra, separated by La(3+) within the lattice. The Re-Re distance within the dimer units is 2.488 A, which is indicative of metal-metal bonding with a bond order of 1.5. The average oxidation state of the Re atom is +5.5, leaving one unpaired electron per dimer unit (S = 1/2). Although the closest interdimer distance is 5.561 A, the magnetic susceptibility data and heat capacity measurements indicate this compound exhibits both short- and long-range magnetic order at surprisingly high temperatures. The zero field cooled (ZFC) magnetic susceptibility data show two broad features at 55 and 105 K, indicating short-range order, and a sharper cusp at 18 K, which signifies long-range antiferromagnetic order. The heat capacity of La(3)Re(2)O(10) shows a lambda-type anomaly at 18 K, which is characteristic of long-range magnetic order. DFT calculations determined that the unpaired electron resides in a pi-bonding orbital and that the unpaired electron density is widely delocalized over the atoms within the dimer, with high values at the bridging oxygens. Extended Hückel spin dimer calculations suggest possible interaction pathways between these dimer units within the crystal lattice. Results from the calculations and fits to the susceptibility data indicate that the short-range magnetic ordering may consist of 1-D antiferromagnetic linear chains of coupled S = 1/2 dimers. The magnetic structure of the antiferromagnetic ground state could not be determined by unpolarized neutron powder diffraction.