Characterization of Deformational Isomerization Potential and Interconversion Dynamics with Ultrafast X-ray Solution Scattering.

Dimeric complexes composed of d8 square planar metal centers and rigid bridging ligands provide model systems to understand the interplay between attractive dispersion forces and steric strain in order to assist the development of reliable methods to model metal dimer complexes more broadly. [Ir2 (dimen)4]2+ (dimen = para-diisocyanomenthane) presents a unique case study for such phenomena, as distortions of the optimal structure of a ligand with limited conformational flexibility counteract the attractive dispersive forces from the metal and ligand to yield a complex with two ground state deformational isomers. Here, we use ultrafast X-ray solution scattering (XSS) and optical transient absorption spectroscopy (OTAS) to reveal the nature of the equilibrium distribution and the exchange rate between the deformational isomers. The two ground state isomers have spectrally distinct electronic excitations that enable the selective excitation of one isomer or the other using a femtosecond duration pulse of visible light. We then track the dynamics of the nonequilibrium depletion of the electronic ground state population─often termed the ground state hole─with ultrafast XSS and OTAS, revealing a restoration of the ground state equilibrium in 2.3 ps. This combined experimental and theoretical study provides a critical test of various density functional approximations in the description of bridged d8-d8 metal complexes. The results show that density functional theory calculations can reproduce the primary experimental observations if dispersion interactions are added, and a hybrid functional, which includes exact exchange, is used.

The magnetic properties of MAl4(OH)12SO4·3H2O with M = Co2+, Ni2+, and Cu2+ determined by a combined experimental and computational approach.

The magnetic properties of the nickelalumite-type layered double hydroxides (LDH), MAl4(OH)12(SO4)·3H2O (MAl4-LDH) with M = Co2+ (S = 3/2), Ni2+ (S = 1), or Cu2+ (S = 1/2) were determined by a combined experimental and computational approach. They represent three new inorganic, low-dimensional magnetic systems with a defect-free, structurally ordered magnetic lattice. They exhibit no sign of magnetic ordering down to 2 K in contrast to conventional hydrotalcite LDH. Detailed insight into the complex interplay between the choice of magnetic ion (M2+) and magnetic properties was obtained by a combination of magnetic susceptibility, heat capacity, neutron scattering, solid-state NMR spectroscopy, and first-principles calculations. The NiAl4- and especially CoAl4-LDH have pronounced zero-field splitting (ZFS, easy-axis and easy-plane, respectively) and weak ferromagnetic nearest-neighbour interactions. Thus, they are rare examples of predominantly zero-dimensional spin systems in dense, inorganic matrices. In contrast, CuAl4-LDH (S = 1/2) consists of weakly ferromagnetic S = 1/2 spin chains. For all three MAl4-LDH, good agreement is found between the experimental magnetic parameters (J, D, g) and first-principles quantum chemical calculations, which also predict that the interchain couplings are extremely weak (< 0.1 cm-1). Thus, our approach will be valuable for evaluation and prediction of magnetic properties in other inorganic materials.

Exploring fingerprints of ultrafast structural dynamics in molecular solutions with an X-ray laser.

We apply ultrashort X-ray laser pulses to track optically excited structural dynamics of [Ir2(dimen)4]2+ molecules in solution. In our exploratory study we determine angular correlations in the scattered X-rays, which comprise a complex fingerprint of the ultrafast dynamics. Model-assisted analysis of the experimental correlation data allows us to elucidate various aspects of the photoinduced changes in the excited molecular ensembles. We unambiguously identify that in our experiment the photoinduced transition dipole moments in [Ir2(dimen)4]2+ molecules are oriented perpendicular to the Ir-Ir bond. The analysis also shows that the ground state conformer of [Ir2(dimen)4]2+ with a larger Ir-Ir distance is mostly responsible for the formation of the excited state. We also reveal that the ensemble of solute molecules can be characterized with a substantial structural heterogeneity due to solvent influence. The proposed X-ray correlation approach offers an alternative path for studies of ultrafast structural dynamics of molecular ensembles in the liquid and gas phases.

Magnetic Archimedean Tessellations in Metal-Organic Frameworks.

The self-assembly of lanthanide ions with ditopic organic spacers results in the formation of complex tiling patterns that mimic the structural motifs of quasi-periodic 2D materials. The linking of trans-{LnI2}+ nodes (Ln = Gd, Dy) by both closed-shell and anion radicals of 4,4'-bipyridine affords rare examples of Archimedean tessellations in a metal-organic framework. We furthermore demonstrate the occurrence of sizable magnetic exchange interactions and slow relaxation of magnetization behavior in a complex tessellation pattern. The implementation of Archimedean tessellations in lanthanide(III) coordination solids couriers a strategy to design elusive quasi-periodic metal-organic frameworks with inimitable magnetic properties.

Evidence for Non-Innocence of a ß-Diketonate Ligand.

ß-Diketonates, such as acetylacetonate, are amongst the most common bidentate ligands towards elements across the entire periodic table and are considered wholly redox-inactive in their complexes. Herein we show that complexation of 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac- ) to CrII spontaneously affords CrIII and a reduced ß-diketonate radical ligand scaffold, as evidenced by crystallographic analysis, magnetic measurements, optical spectroscopy, reactivity studies, and DFT calculations. The possibility of harnessing ß-diketonates as electron reservoirs opens up possibilities for new metal-ligand concerted reactivity in the ubiquitous ß-diketonate coordination chemistry.

Structural characterization and magnetic properties of chromium jarosite KCr3(OD)6(SO4)2.

Potassium chromium jarosite, KCr3(OH)6(SO4)2 (Cr-jarosite), is considered a promising candidate to display spin liquid behavior due to the strong magnetic frustration imposed by the crystal structure. However, the ground state magnetic properties have been debated, since Cr-jarosite is notoriously non-stoichiometric. Our study reports the magnetic properties for deuterated KCr3(OD)6(SO4)2 on chemically well-defined samples, which have been characteried by a combination of powder X-ray diffraction, neutron diffraction, solid state NMR spectroscopy, and scanning electron microscopy with energy dispersive spectroscopy. Eight polycrystalline samples, which all contained only 1-3% Cr vacancies were obtained. However, significant substitution (2-27%) of potassium with H2O and/or H3O+ was observed and resulted in pronounced stacking disorder along the c-axis. A clear second-order transition to an antiferromagnetically ordered phase at TN = 3.8(1) K with a small net moment of 0.03 µB per Cr3+-ion was obtained from vibrating sample magnetometry and temperature dependent neutron diffraction. The moment is attributed to spin canting caused by the Dzyaloshinskii-Moriya interaction. Thus, our experimental results imply that even ideal potassium chromium jarosite will exhibit magnetic order below 4 K and therefore it does not qualify as a true spin liquid material.

Coercive Fields Above 6†T in Two Cobalt(II)-Radical Chain Compounds.

Lanthanide permanent magnets are widely used in applications ranging from nanotechnology to industrial engineering. However, limited access to the rare earths and rising costs associated with their extraction are spurring interest in the development of lanthanide-free hard magnets. Zero- and one-dimensional magnetic materials are intriguing alternatives due to their low densities, structural and chemical versatility, and the typically mild, bottom-up nature of their synthesis. Here, we present two one-dimensional cobalt(II) systems Co(hfac)2 (R-NapNIT) (R-NapNIT=2-(2'-(R-)naphthyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, R=MeO or EtO) supported by air-stable nitronyl nitroxide radicals. These compounds are single-chain magnets and exhibit wide, square magnetic hysteresis below 14 K, with giant coercive fields up to 65 or 102 kOe measured using static or pulsed high magnetic fields, respectively. Magnetic, spectroscopic, and computational studies suggest that the record coercivities derive not from three-dimensional ordering but from the interaction of adjacent chains that compose alternating magnetic sublattices generated by crystallographic symmetry.

Access to Heteroleptic Fluorido-Cyanido Complexes with a Large Magnetic Anisotropy by Fluoride Abstraction.

Silicon-mediated fluoride abstraction is demonstrated as a means of generating the first fluorido-cyanido transition metal complexes. This new synthetic approach is exemplified by the synthesis and characterization of the heteroleptic complexes, trans-[MIV F4 (CN)2 ]2- (M=Re, Os), obtained from their homoleptic [MIV F6 ]2- parents. As shown by combined high-field electron paramagnetic resonance spectroscopy and magnetization measurements, the partial substitution of fluoride by cyanide ligands leads to a marked increase in the magnetic anisotropy of trans-[ReF4 (CN)2 ]2- as compared to [ReF6 ]2- , reflecting the severe departure from an ideal octahedral (Oh point group) ligand field. This methodology paves the way toward the realization of new heteroleptic transition metal complexes that may be used as highly anisotropic building-blocks for the design of high-performance molecule-based magnetic materials.

[UF6 ]2- : A Molecular Hexafluorido Actinide(IV) Complex with Compensating Spin and Orbital Magnetic Moments.

The first structurally characterized hexafluorido complex of a tetravalent actinide ion, the [UF6 ]2- anion, is reported in the (NEt4 )2 [UF6 ]⋅2 H2 O salt (1). The weak magnetic response of 1 results from both UIV spin and orbital contributions, as established by combining X-ray magnetic circular dichroism (XMCD) spectroscopy and bulk magnetization measurements. The spin and orbital moments are virtually identical in magnitude, but opposite in sign, resulting in an almost perfect cancellation, which is corroborated by ab initio calculations. This work constitutes the first experimental demonstration of a seemingly non-magnetic molecular actinide complex carrying sizable spin and orbital magnetic moments.

Coherent Manipulation of a Molecular Ln-Based Nuclear Qudit Coupled to an Electron Qubit.

We demonstrate that the [Yb(trensal)] molecule is a prototypical coupled electronic qubit-nuclear qudit system. The combination of noise-resilient nuclear degrees of freedom and large reduction of nutation time induced by electron-nuclear mixing enables coherent manipulation of this qudit by radio frequency pulses. Moreover, the multilevel structure of the qudit is exploited to encode and operate a qubit with embedded basic quantum error correction.

[OsF6 ]x- : Molecular Models for Spin-Orbit Entangled Phenomena.

Heavy 5d elements, like osmium, feature strong spin-orbit interactions which are at the origin of exotic physical behaviors. Revealing the full potential of, for example, novel osmium oxide materials ("osmates") is however contingent upon a detailed understanding of the local single-ion properties. Herein, two molecular osmate analogues, [OsF6 ]2- and [OsF6 ]- , are reported as model systems for Os4+ and Os5+ centers found in oxides. Using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) techniques, combined with state-of-the-art ab initio calculations, their ground state was elucidated; mirroring the osmium electronic structure in osmates. The realization of such molecular model systems provides a unique chemical playground to engineer materials exhibiting spin-orbit entangled phenomena.

Toward Molecular 4f Single-Ion Magnet Qubits.

Quantum coherence is detected in the 4f single-ion magnet (SIM) Yb(trensal), by isotope selective pulsed EPR spectroscopy on an oriented single crystal. At X-band, the spin-lattice relaxation (T1) and phase memory (Tm) times are found to be independent of the nuclei bearing, or not, a nuclear spin. The observation of Rabi oscillations of the spin echo demonstrates the possibility to coherently manipulate the system for more than 70 rotations. This renders Yb(trensal), a sublimable and chemically modifiable SIM, an excellent candidate for quantum information processing.

Spin Crossover in Fe(II) Complexes with N4S2 Coordination.

Reactions of Fe(II) precursors with the tetradentate ligand S,S'-bis(2-pyridylmethyl)-1,2-thioethane (bpte) and monodentate NCE(-) coligands afforded mononuclear complexes [Fe(bpte)(NCE)2] (1, E = S; 2, E = Se; 3, E = BH3) that exhibit temperature-induced spin crossover (SCO). As the ligand field strength increases from NCS(-) to NCSe(-) to NCBH3(-), the SCO shifts to higher temperatures. Complex 1 exhibits only a partial (15%) conversion from the high-spin (HS) to the low-spin (LS) state, with an onset around 100 K. Complex 3 exhibits a complete SCO with T1/2 = 243 K. While the γ-2 polymorph also shows the complete SCO with T1/2 = 192 K, the α-2 polymorph exhibits a two-step SCO with the first step leading to a 50% HS → LS conversion with T1/2 = 120 K and the second step proceeding incompletely in the 80-50 K range. The amount of residual HS fraction of α-2 that remains below 60 K depends on the cooling rate. Fast flash-cooling allows trapping of as much as 45% of the HS fraction, while slow cooling leads to a 14% residual HS fraction. The slowly cooled sample of α-2 was subjected to irradiation in the magnetometer cavity resulting in a light-induced excited spin state trapping (LIESST) effect. As demonstrated by Mössbauer spectroscopy, an HS fraction of up to 85% could be achieved by irradiation at 4.2 K.

Cyanide Single-Molecule Magnets Exhibiting Solvent Dependent Reversible "On" and "Off" Exchange Bias Behavior.

The syntheses, structures, and magnetic properties of four new complex salts, (PPN){[Mn(III)(salphen)(MeOH)]2[M(III)(CN)6]}·7MeOH (Mn2M·7MeOH) (M = Fe, Ru, Os and Co; PPN(+) = bis(triphenylphosphoranylidene)ammonium cation; H2salphen = N,N'-bis(salicylidene)-1,2-diaminobenzene), and a mixed metal Co/Os analogue (PPN){[Mn(III)(salphen)(MeOH)]2[Co(III)0.92Os(III)0.08(CN)6]}·7MeOH were undertaken. It was found that all compounds exhibit switchable single-molecule magnet (SMM) and exchange-bias behavior depending on the interstitial methanol content. The pristine (PPN){[Mn(salphen)(MeOH)]2[Os(CN)6]}·7MeOH (Mn2Os·7MeOH) behaves as an SMM with an effective barrier for the magnetization reversal, (Ueff/kB), of 17.1 K. Upon desolvation, Mn2Os exhibits an increase of Ueff/kB to 42.0 K and an opening of the hysteresis loop observable at 1.8 K. Mn2Os·7MeOH shows also exchange-bias behavior with magnetic hysteresis loops exhibiting a shift in the quantum tunneling to 0.25 T from zero-field. The Fe(III) and Ru(III) analogues were prepared as reference compounds for assessing the effect of the 5d versus 4d and 3d metal ions on the SMM properties. These compounds are also SMMs and exhibit similar effects but with lower energy barriers. These findings underscore the importance of introducing heavy transition elements into SMMs to improve their slow relaxation of the magnetization properties. The (PPN){[Mn(III)(salphen)(MeOH)]2[Co(III)(CN)6]}·7MeOH (Mn2Co·7MeOH) analogue with a diamagnetic Co(III) central atom and the mixed Co/Os (PPN){[Mn(III)(salphen)(MeOH)]2[Co(III)0.92Os(III)0.08(CN)6]}·7MeOH (Mn2Co/Os·7MeOH) "magnetically diluted" system with a 9:1 Co/Os metal ratio were prepared in order to further probe the nature of the energy barrier increase upon desolvation of Mn2Os. In addition, inelastic neutron scattering and frequency-domain Fourier-transform THz electron paramagnetic resonance spectra obtained on Mn2Os·7MeOH and Mn2Os in combination with the magnetic data revealed the presence of anisotropic exchange interactions between Mn(III) and Os(III) ions.

Design of Single-Molecule Magnets: Insufficiency of the Anisotropy Barrier as the Sole Criterion.

Determination of the electronic energy spectrum of a trigonal-symmetry mononuclear Yb(3+) single-molecule magnet (SMM) by high-resolution absorption and luminescence spectroscopies reveals that the first excited electronic doublet is placed nearly 500 cm(-1) above the ground one. Fitting of the paramagnetic relaxation times of this SMM to a thermally activated (Orbach) model {τ = τ0 × exp[ΔOrbach/(kBT)]} affords an activation barrier, ΔOrbach, of only 38 cm(-1). This result is incompatible with the spectroscopic observations. Thus, we unambiguously demonstrate, solely on the basis of experimental data, that Orbach relaxation cannot a priori be considered as the main mechanism determining the spin dynamics of SMMs. This study highlights the fact that the general synthetic approach of optimizing SMM behavior by maximization of the anisotropy barrier, intimately linked to the ligand field, as the sole parameter to be tuned, is insufficient because of the complete neglect of the interaction of the magnetic moment of the molecule with its environment. The Orbach mechanism is expected dominant only in the cases in which the energy of the excited ligand field state is below the Debye temperature, which is typically low for molecular crystals and, thus, prevents the use of the anisotropy barrier as a design criterion for the realization of high-temperature SMMs. Therefore, consideration of additional design criteria that address the presence of alternative relaxation processes beyond the traditional double-well picture is required.

[Cr(III)8M(II)6](12+) Coordination Cubes (M(II)=Cu, Co).

[Cr(III)8M(II)6](12+) (M(II) =Cu, Co) coordination cubes were constructed from a simple [Cr(III) L3 ] metalloligand and a "naked" M(II) salt. The flexibility in the design proffers the potential to tune the physical properties, as all the constituent parts of the cage can be changed without structural alteration. Computational techniques (known in theoretical nuclear physics as statistical spectroscopy) in tandem with EPR spectroscopy are used to interpret the magnetic behavior.

Magnetic interactions through fluoride: magnetic and spectroscopic characterization of discrete, linearly bridged [Mn(III)2(µ-F)F4(Me3tacn)2](PF6).

The nature of the magnetic interaction through fluoride in a simple, dinuclear manganese(III) complex (1), bridged by a single fluoride ion in a perfectly linear fashion, is established by experiment and density functional theory. The magnitude of the antiferromagnetic exchange interaction and the manganese(III) zero-field-splitting parameters are unambiguously determined by inelastic neutron scattering to yield J = 33.0(2) cm(-1) (H = JS1·S2 Hamiltonian definition) and single-ion D = -4.0(1) cm(-1). Additionally, high-field, high-frequency electron paramagnetic resonance and magnetic measurements support the parameter values and resolve |E| ≈ 0.04 cm(-1). The exchange coupling constant (J) is 1 order of magnitude smaller than that found in comparable systems with linear oxide bridging but comparable to typical magnitudes through cyanide, thus underlining the potential of fluoride complexes as promising building blocks for novel magnetic systems.

Social-, age- and gender differences in testing and positive rates for Chlamydia trachomatis urogenital infection - a register-based study.

BACKGROUND: Chlamydia trachomatis is suspected of causing female infertility. It is the most widespread sexually transmitted infection with an estimated general prevalence of ~5-10% with a peak in younger individuals. C. trachomatis infection is more prevalent among lower social classes. OBJECTIVE: In this study, the association between age, gender, social status and testing and positive rates is investigated in the age group 15-24 years. DESIGN: Case-control study linked to data from Statistics Denmark. METHODS: Data from the Department of Microbiology, Hvidovre University Hospital, Copenhagen were used and included 21887 people tested by general practitioners (GPs) and 3177 people tested at a venereological clinic. The age range was 15-24 years in 2011. These data were linked with the parental educational status delivered by Statistics Denmark, which also delivered a matched control group. The data were analysed using a case-control design. RESULTS: Testing was more frequent in the following groups: age range 20-24 years, females and patients with higher parental educational status. About 87.3% of patient had been tested by GPs. Positive rates were highest among males at the general practice constituting 17.1% versus females 10.6%, younger individuals and patients with lower parental educational status. CONCLUSIONS: The C. trachomatis testing pattern and positive rates highlight a need for a greater focus on males, younger patients and individuals with a lower social status.

Fluoride-bridged {Gd(III)3M(III)2} (M = Cr, Fe, Ga) molecular magnetic refrigerants.

The reaction of fac-[M(III)F3(Me3tacn)]⋅x H2O with Gd(NO3)3⋅5H2O affords a series of fluoride-bridged, trigonal bipyramidal {Gd(III)3M(III)2} (M = Cr (1), Fe (2), Ga (3)) complexes without signs of concomitant GdF3 formation, thereby demonstrating the applicability even of labile fluoride-complexes as precursors for 3d-4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight ligand sphere, gives rise to large magnetic entropy changes of 38.3 J kg(-1) K(-1) (1) and 33.1 J kg(-1) K(-1) (2) for the field change 7 T→0 T. Interestingly, the entropy change, and the magnetocaloric effect, are smaller in 2 than in 1 despite the larger spin ground state of the former secured by intramolecular Fe-Gd ferromagnetic interactions. This observation underlines the necessity of controlling not only the ground state but also close-lying excited states for successful design of molecular refrigerants.

[ReF(6)](2-) : a robust module for the design of molecule-based magnetic materials.

A facile synthesis of the [ReF6 ](2-) ion and its use as a building block to synthesize magnetic systems are reported. Using dc and ac magnetic susceptibility measurements, INS and EPR spectroscopies, the magnetic properties of the isolated [ReF6 ](2-) unit in (PPh4 )2 [ReF6 ]⋅2 H2 O (1) have been fully studied including the slow relaxation of the magnetization observed below ca. 4 K. This slow dynamic is preserved for the one-dimensional coordination polymer [Zn(viz)4 (ReF6 )]∞ (2, viz=1-vinylimidazole), demonstrating the irrelevance of low symmetry for such magnetization dynamics in systems with easy-plane-type anisotropy. The ability of fluoride to mediate significant exchange interactions is exemplified by the isostructural [Ni(viz)4 (ReF6 )]∞ (3) analogue in which the ferromagnetic Ni(II) -Re(IV) interaction (+10.8 cm(-1) ) dwarfs the coupling present in related cyanide-bridged systems. These results reveal [ReF6 ](2-) to be an unique new module for the design of molecule-based magnetic materials.