Confining single Er3+ ions in sub-3 nm NaYF4 nanoparticles to induce slow relaxation of the magnetisation.

Molecular systems known as single-molecule magnets (SMMs) exhibit magnet-like behaviour of slow relaxation of the magnetisation and magnetic hysteresis and have potential application in high-density memory storage or quantum computing. Often, their intrinsic magnetic properties are plagued by low-energy molecular vibrations that lead to phonon-induced relaxation processes, however, there is no straightforward synthetic approach for molecular systems that would lead to a small amount of low-energy vibrations and low phonon density of states at the spin-resonance energies. In this work, we apply knowledge accumulated over the last decade in molecular magnetism to nanoparticles, incorporating Er3+ ions in an ultrasmall sub-3 nm diamagnetic NaYF4 nanoparticle (NP) and probing the slow relaxation dynamics intrinsic to the Er3+ ion. Furthermore, by increasing the doping concentration, we also investigate the role of intraparticle interactions within the NP. The knowledge gained from this study is anticipated to enable better design of magnetically high-performance molecular and bulk magnets for a wide variety of applications, such as molecular electronics.

Synthesis, characterisation and reactivity of a zinc triazenide for potential use in vapour deposition.

In this study, we synthesised and characterised a new zinc(II) triazenide for potential use in vapour deposition of zinc sulphide thin films. The compound is volatile and quantitatively sublimes at 80 °C under vacuum (0.5 mbar). Thermogravimetric analysis showed a one-step volatilisation with an onset temperature at ∼125 °C and 5% residual mass. The compound also reacted with 2 or 4 molar equivalents of triphenylsilanethiol to give dimeric and monomeric zinc thiolates, respectively. The high volatility, thermal stability, and reactivity with sterically hindered thiols makes this compound a potential candidate for use in vapour deposition of zinc containing thin films.

α-Aminophosphonates, -Phosphinates, and -Phosphine Oxides as Extraction and Precipitation Agents for Rare Earth Metals, Thorium, and Uranium: A Review.

α-Aminophosphonates, -phosphinates, and -phosphine oxides are a group of organophosphorus compounds that were investigated as extraction agents for rare earth (RE) metals and actinoids for the first time in the 1960s. However, more systematic investigations of their extraction properties towards REs and actinoids were not started until the 2010s. Indeed, recent studies have shown that these α-amino-functionalized compounds can outperform the commercial organophosphorus extraction agents in RE separations. They have also proven to be very efficient extraction and precipitation agents for recovering Th and U from RE concentrates. These actinoids coexist with REs in some of the commercially important RE-containing minerals. The efficient separation and purification of REs is becoming more and more important every year as these elements have a pivotal role in many existing technologies. If one also considers the facile synthesis of α-amino-functionalized organophosphorus extractants and precipitation agents, it is expected that they will be increasingly utilized in the extraction chemistry of REs and actinoids in the future. This review collates α-aminophosphonates, -phosphinates, and -phosphine oxides that have been utilized in the separation chemistry of REs and actinoids, including their most relevant synthetic routes and molecular properties. Their extraction and precipitation properties towards REs and actinoids are also discussed.

A diamagnetic iron complex and its twisted sister - structural evidence on partial spin state change in a crystalline iron complex.

We report here the syntheses of a diamagnetic Fe complex [Fe(HL)2] (1), prepared by reacting a redox non-innocent ligand precursor N,N'-bis(3,5-di-tert-butyl-2-hydroxy-phenyl)-1,2-phenylenediamine (H4L) with FeCl3, and its phenoxazine derivative [Fe(L')2] (2), which was obtained via intra-ligand cyclisation of the parent complex. Magnetic measurements, accompanied by spectroscopic, structural and computational analyses show that 1 can be viewed as a rather unusual Fe(III) complex with a diamagnetic ground state in the studied temperature range due to a strong antiferromagnetic coupling between the low-spin Fe(III) ion and a radical ligand. For a paramagnetic high-spin Fe(II) complex 2 it was found that, when crystalline, it undergoes a thermally induced process where 25% of the molecules in the material change to a diamagnetic low-spin ground state below 100 K. Single crystal X-ray studies conducted at 95 K afforded detailed structural evidence for this partial change of spin state of 2 showing the existence of crystallographically distinct molecules in a 3 : 1 ratio which exist in high- and low-spin states, respectively. Also, the magnetic behaviour of 2 was found to be related with the crystallinity of the material as demonstrated by near-IR radiation to unpaired electrons conversion ability of amorphous sample of 2.

Alkyl-Substituted Aminobis(phosphonates)-Efficient Precipitating Agents for Rare Earth Elements, Thorium, and Uranium in Aqueous Solutions.

The efficient and environmentally sustainable separation process for rare earth elements (REE), especially for adjacent lanthanoids, remains a challenge due to the chemical similarity of REEs. Tetravalent actinoids, thorium, and traces of uranium are also present in concentrates of REEs, making their separation relevant. This study reports six simple water-soluble aminobis(phosphonate) ligands, RN[CH2P(O)(OH)2]2 (1 R = CH2CH3, 2 R = (CH2)2CH3, 3 R = (CH2)3CH3, 4 R = (CH2)4CH3, 5 R = (CH2)5CH3, 6 R = CH2CH(C2H5)(CH2)3CH3) as precipitating agents for REEs, Th, and U, as well as gives insight into the coordination modes of the utilized ligands with REEs at the molecular level. Aminobis(phosphonates) 4-6 with longer carbon chains were found to separate selectively thorium, uranium, and scandium from REEs with short precipitation time (15 min) and excellent separation factors that generally range from 100 to 2000 in acidic aqueous solution. Ligands 1-6 also improved separation factors for adjacent lanthanoids in comparison to traditional oxalate precipitation agents. Importantly, precipitated metals can be recovered from the ligands with 3 molar HNO3 with no observed ligand decomposition enabling the possibility of recycling the ligands in the separation process. NMR-monitored pH titrations for 1 showed deprotonation steps at pK a 1.3, 5.55, and >10.5, which indicate that the ligands remain in a deprotonated [L]-1 form in the pH range of 0-4 used in the precipitation studies. 31P NMR titration studies between 1 and M(NO3)3 (M = Y, La, Lu) gave satisfactory fits for 1:3, 1:2, and 1:1 metal-ligand stoichiometries for Y, La, and Lu, respectively, according to an F-test. Therefore, aminobis(phosphonate) precipitation agents 1-6 are likely to form metal complexes with fewer ligands than traditional separation agents like DEHPA, which coordinates to REEs in 1:6 metal-ligand ratio.

Probing optical and magnetic properties via subtle stereoelectronic effects in mononuclear DyIII-complexes.

Tapping into the secondary coordination environment of mononuclear DyIII-complexes leads to drastic changes in luminescence and magnetism. Visualization of effects induced by stereoelectronics on the opto-magnetic properties was achieved through subtle modifications in the ligand framework.

Asymmetric Ring Opening in a Tetrazine-Based Ligand Affords a Tetranuclear Opto-Magnetic Ytterbium Complex.

We report the formation of a tetranuclear lanthanide cluster, [Yb4 (bpzch)2 (fod)10 ] (1), which occurs from a serendipitous ring opening of the functionalised tetrazine bridging ligand, bpztz (3,6-dipyrazin-2-yl-1,2,4,5-tetrazine) upon reacting with Yb(fod)3 (fod- =6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octandionate). Compound 1 was structurally elucidated via single-crystal X-ray crystallography and subsequently magnetically and spectroscopically characterised to analyse its magnetisation dynamics and its luminescence behaviour. Computational studies validate the observed MJ energy levels attained by spectroscopy and provides a clearer picture of the slow relaxation of the magnetisation dynamics and relaxation pathways. These studies demonstrate that 1 acts as a single-molecule magnet (SMM) under an applied magnetic field in which the relaxation occurs via a combination of Raman, direct, and quantum tunnelling processes, a behaviour further rationalised analysing the luminescent properties. This marks the first lanthanide-containing molecule that forms by means of an asymmetric tetrazine decomposition.

Anion-driven encapsulation of cationic guests inside pyridine[4]arene dimers.

Pyridine[4]arenes have previously been considered as anion binding hosts due to the electron-poor nature of the pyridine ring. Herein, we demonstrate the encapsulation of Me4N+ cations inside a dimeric hydrogen-bonded pyridine[4]arene capsule, which contradicts with earlier assumptions. The complexation of a cationic guest inside the pyridine[4]arene dimer has been detected and studied by multiple gas-phase techniques, ESI-QTOF-MS, IRMPD, and DT-IMMS experiments, as well as DFT calculations. The comparison of classical resorcinarenes with pyridinearenes by MS and NMR experiments reveals clear differences in their host-guest chemistry and implies that cation encapsulation in pyridine[4]arene is an anion-driven process.

Triplet-State Position and Crystal-Field Tuning in Opto-Magnetic Lanthanide Complexes: Two Sides of the Same Coin.

Lanthanide-complex-based luminescence thermometry and single-molecule magnetism are two effervescent fields of research, owing to the great promise they hold from an application standpoint. The high thermal sensitivity achievable, their contactless nature, along with sub-micrometric spatial resolution make these luminescent thermometers appealing for accurate temperature probing in miniaturised electronics. To that end, single-molecule magnets (SMMs) are expected to revolutionise the field of spintronics, thanks to the improvements made in terms of their working temperature-now surpassing that of liquid nitrogen-and manipulation of their spin state. Hence, the combination of such opto-magnetic properties in a single molecule is desirable in the aim of overcoming, among others, addressability issues. Yet, improvements must be made through design strategies for the realisation of the aforementioned goal. Moving forward from these considerations, we present a thorough investigation of the effect that changes in the ligand scaffold of a family of terbium complexes have on their performance as luminescent thermometers and SMMs. In particular, an increased number of electron-withdrawing groups yields modifications of the metal coordination environment and a lowering of the triplet state of the ligands. These effects are tightly intertwined, thus, resulting in concomitant variations of the SMM and the luminescence thermometry behaviour of the complexes. Supported by ab initio calculations, we can rationally interpret the observed trends and provide solid foundations for the development of opto-magnetic lanthanide complexes.

A Luminescent Thermometer Exhibiting Slow Relaxation of the Magnetization: Toward Self-Monitored Building Blocks for Next-Generation Optomagnetic Devices.

The development and integration of Single-Molecule Magnets (SMMs) into molecular electronic devices continue to be an exciting challenge. In such potential devices, heat generation due to the electric current is a critical issue that has to be considered upon device fabrication. To read out accurately the temperature at the submicrometer spatial range, new multifunctional SMMs need to be developed. Herein, we present the first self-calibrated molecular thermometer with SMM properties, which provides an elegant avenue to address these issues. The employment of 2,2'-bipyrimidine and 1,1,1-trifluoroacetylacetonate ligands results in a dinuclear compound, [Dy2(bpm)(tfaa)6], which exhibits slow relaxation of the magnetization along with remarkable photoluminescent properties. This combination allows the gaining of fundamental insight in the electronic properties of the compound and investigation of optomagnetic cross-effects (Zeeman effect). Importantly, spectral variations stemming from two distinct thermal-dependent mechanisms taking place at the molecular level are used to perform luminescence thermometry over the 5-398 K temperature range. Overall, these properties make the proposed system a unique molecular luminescent thermometer bearing SMM properties, which preserves its temperature self-monitoring capability even under applied magnetic fields.

Thermodynamically driven self-assembly of pyridinearene to hexameric capsules.

Pyridinearene macrocycles have previously shown unique host-guest properties in their capsular dimers including endo complexation of neutral molecules and exo complexation of anions. Here, we demonstrate for the first time the formation of hydrogen bonded hexamer of tetraisobutyl-octahydroxypyridinearene in all three states of matter - gas phase, solution and solid-state. Cationic tris(bipyridine)ruthenium(ii) template was found to stabilize the hexamer in gas phase, whereas solvent molecules do this in condensed phases. In solution, the capsular hexamer was found to be the thermodynamically favoured self-assembly product and transition from dimer to hexamer occurred in course of time. The crystal structure of hexamer revealed 24 N-HO direct intermolecular hydrogen bonds between the six pyridinearene macrocycles without any bridging solvent molecules. Hydrogen bond patterns correlate well with DFT computed structures. Thus, all structural chemistry methods (IM-MS, DOSY NMR, DFT, X-ray crystallography) support the same structure of the hexameric capsule that has a diameter of ca. 3 nm and volume of 1160 Å3.

Antipsychotic and benzodiazepine use and brain morphology in schizophrenia and affective psychoses - Systematic reviews and birth cohort study.

The aim of this paper was to investigate differences in brain structure volumes between schizophrenia and affective psychoses, and whether cumulative lifetime antipsychotic or benzodiazepine doses relate to brain morphology in these groups. We conducted two systematic reviews on the topic and investigated 44 schizophrenia cases and 19 with affective psychoses from the Northern Finland Birth Cohort 1966. The association between lifetime antipsychotic and benzodiazepine dose and brain MRI scans at the age of 43 was investigated using linear regression. Intracranial volume, sex, illness severity, and antipsychotic/benzodiazepine doses were used as covariates. There were no differences between the groups in brain structure volumes. In schizophrenia, after adjusting for benzodiazepine dose and symptoms, a negative association between lifetime antipsychotic dose and the nucleus accumbens volume remained. In affective psychoses, higher lifetime benzodiazepine dose associated with larger volumes of total gray matter and hippocampal volume after controlling for antipsychotic use and symptoms. It seems that in addition to antipsychotics, the severity of symptoms and benzodiazepine dose are also associated with brain structure volumes. These results suggest, that benzodiazepine effects should also be investigated also independently and not only as a confounder.

Synthesis, Stability and Relaxivity of TEEPO-Met: An Organic Radical as a Potential Tumour Targeting Contrast Agent for Magnetic Resonance Imaging.

Cancer is a widespread and life-threatening disease and its early-stage diagnosis is vital. One of the most effective, non-invasive tools in medical diagnostics is magnetic resonance imaging (MRI) with the aid of contrast agents. Contrast agents that are currently in clinical use contain metals, causing some restrictions in their use. Also, these contrast agents are mainly non-specific without any tissue targeting capabilities. Subsequently, the interest has notably increased in the research of organic, metal-free contrast agents. This study presents a new, stable organic radical, TEEPO-Met, where a radical moiety 2,2,6,6-tetraethylpiperidinoxide (TEEPO) is attached to an amino acid, methionine (Met), as a potentially tumour-targeting moiety. We describe the synthesis, stability assessment with electron paramagnetic resonance (EPR) spectroscopy and relaxation enhancement abilities by an in vitro nuclear magnetic resonance (NMR) and phantom MRI studies of TEEPO-Met. The new compound proved to be stable notably longer than the average imaging time in conditions mimicking a biological matrix. Also, it significantly reduced the relaxation times of water, making it a promising candidate as a novel tumour targeting contrast agent for MRI.

Thermal expansion and magnetic properties of benzoquinone-bridged dinuclear rare-earth complexes.

The synthesis and structural characterization of two benzoquinone-bridged dinuclear rare-earth complexes [BQ(MCl2·THF3)2] (BQ = 2,5-bisoxide-1,4-benzoquinone; M = Y (1), Dy (2)) are described. Of these reported metal complexes, the dysprosium analogue 2 is the first discrete bridged dinuclear lanthanide complex in which both metal centres reside in pentagonal bipyramidal environments. Interestingly, both complexes undergo significant thermal expansion upon heating from 120 K to 293 K as illustrated by single-crystal X-ray and powder diffraction experiments. AC magnetic susceptibility measurements reveal that 2 does not show the slow relation of magnetization in zero dc field. The absent of single-molecule behaviour in 2 arises from the rotation of the principal magnetic axis as compared to the pseudo-C5 axis of the pentagonal bipyramidal environment as suggested by ab initio calculations. The cyclic voltammetry and chemical reduction experiments demonstrated that complexes 1 and 2 can be reduced to radical species containing [BQ3˙-]. This study establishes efficient synthetic strategy to make bridged redox-active multinuclear lanthanide complexes with a pentagonal bipyramidal coordination environment that are potential precursors for single-molecule magnets.

Simultaneous endo and exo†Complex Formation of Pyridine[4]arene Dimers with Neutral and Anionic Guests.

The formation of complexes between hexafluorophosphate (PF6- ) and tetraisobutyloctahydroxypyridine[4]arene has been thoroughly studied in the gas phase (ESI-QTOF-MS, IM-MS, DFT calculations), in the solid state (X-ray crystallography), and in chloroform solution (1 H, 19 F, and DOSY NMR spectroscopy). In all states of matter, simultaneous endo complexation of solvent molecules and exo complexation of a PF6- anion within a pyridine[4]arene dimer was observed. While similar ternary complexes are often observed in the solid state, this is a unique example of such behavior in the gas phase.

Long-term antipsychotic and benzodiazepine use and brain volume changes in schizophrenia: The Northern Finland Birth Cohort 1966 study.

High doses of antipsychotics have been associated with loss in cortical and total gray matter in schizophrenia. However, previous imaging studies have not taken benzodiazepine use into account, in spite of evidence suggesting adverse effects such as cognitive impairment and increased mortality. In this Northern Finland Birth Cohort 1966 study, 69 controls and 38 individuals with schizophrenia underwent brain MRI at the ages of 34 and 43 years. At baseline, the average illness duration was over 10 years. Brain structures were delineated using an automated volumetry system, volBrain, and medication data on cumulative antipsychotic and benzodiazepine doses were collected using medical records and interviews. We used linear regression with intracranial volume and sex as covariates; illness severity was also taken into account. Though both medication doses associated to volumetric changes in subcortical structures, after adjusting for each other and the average PANSS total score, higher scan-interval antipsychotic dose associated only to volume increase in lateral ventricles and higher benzodiazepine dose associated with volume decrease in the caudate nucleus. To our knowledge, there are no previous studies reporting associations between benzodiazepine dose and brain structural changes. Further studies should focus on how these observations correspond to cognition and functioning.

Lifetime antipsychotic medication and cognitive performance in schizophrenia at age 43 years in a general population birth cohort.

This naturalistic study analysed the association between cumulative lifetime antipsychotic dose and cognition in schizophrenia after an average of 16.5 years of illness. Sixty participants with schizophrenia and 191 controls from the Northern Finland Birth Cohort 1966 were assessed at age 43 years with a neurocognitive test battery. Cumulative lifetime antipsychotic dose-years were collected from medical records and interviews. The association between antipsychotic dose-years and a cognitive composite score based on principal component analysis was analysed using linear regression. Higher lifetime antipsychotic dose-years were significantly associated with poorer cognitive composite score, when adjusted for gender, onset age and lifetime hospital treatment days. The effects of typical and atypical antipsychotics did not differ. This is the first report of an association between cumulative lifetime antipsychotic dose and global cognition in midlife schizophrenia. Based on these data, higher lifetime antipsychotic dose-years may be associated with poorer cognitive performance at age 43 years. Potential biases related to the naturalistic design may partly explain the results; nonetheless, it is possible that large antipsychotic doses harm cognition in schizophrenia in the long-term.

Strong Exchange Coupling in a Trimetallic Radical-Bridged Cobalt(II)-Hexaazatrinaphthylene Complex.

Reducing hexaazatrinaphthylene (HAN) with potassium in the presence of 18-c-6 produces [{K(18-c-6)}HAN], which contains the S=1/2 radical [HAN](.-) . The [HAN](.-) radical can be transferred to the cobalt(II) amide [Co{N(SiMe3 )2 }2 ], forming [K(18-c-6)][(HAN){Co(N'')2 }3 ]; magnetic measurements on this compound reveal an S=4 spin system with strong cobalt-ligand antiferromagnetic exchange and J≈-290 cm(-1) (-2 J formalism). In contrast, the Co(II) centres in the unreduced analogue [(HAN){Co(N'')2 }3 ] are weakly coupled (J≈-4.4 cm(-1) ). The finding that [HAN](.-) can be synthesized as a stable salt and transferred to cobalt introduces potential new routes to magnetic materials based on strongly coupled, triangular HAN building blocks.

Use of psychiatric medications in schizophrenia and other psychoses in a general population sample.

The information on the use of psychiatric medications in general population-based samples is limited. Our aim was to analyse the use of psychiatric medications and factors associated with antipsychotic use in psychoses in a general population sample. Fifty-five persons with schizophrenia, 21 with bipolar psychosis or psychotic depression and 20 with other psychoses from the Northern Finland Birth Cohort 1966 were examined at about 43 years of age. The frequency of use and dosage of psychiatric medication and the factors associated with the use of antipsychotics were analysed. Antipsychotics were used by 85% of schizophrenia, 65% of bipolar psychosis or psychotic depression and 62% of other psychoses cases; antidepressants were used by 22%, 60% and 33%; and benzodiazepines by 42%, 35% and 10%, respectively. In all the diagnostic groups, higher symptom scores and a higher number of hospital days were associated with the use of antipsychotics. In schizophrenia and other psychoses, poorer social and occupational functioning, and in other psychoses, female gender and lower education were also associated with the use of antipsychotics. Our results may partly indicate that, especially in schizophrenia, the effectiveness of antipsychotics is not as good as expected.