Highly Occupied Surface States at Deuterium-Grown Boron-Doped Diamond Interfaces for Efficient Photoelectrochemistry.

Polycrystalline boron-doped diamond is a promising material for high-power aqueous electrochemical applications in bioanalytics, catalysis, and energy storage. The chemical vapor deposition (CVD) process of diamond formation and doping is totally diversified by using high kinetic energies of deuterium substituting habitually applied hydrogen. The high concentration of deuterium in plasma induces atomic arrangements and steric hindrance during synthesis reactions, which in consequence leads to a preferential (111) texture and more effective boron incorporation into the lattice, reaching a one order of magnitude higher density of charge carriers. This provides the surface reconstruction impacting surficial populations of CC dimers, CH, CO groups, and COOH termination along with enhanced kinetics of their abstraction, as revealed by high-resolution core-level spectroscopies. A series of local densities of states were computed, showing a rich set of highly occupied and localized surface states for samples deposited in deuterium, negating the connotations of band bending. The introduction of enhanced incorporation of boron into (111) facet of diamond leads to the manifestation of surface electronic states below the Fermi level and above the bulk valence band edge. This unique electronic band structure affects the charge transfer kinetics, electron affinity, and diffusion field geometry critical for efficient electrolysis, electrocatalysis, and photoelectrochemistry.

Vibrational Properties of LaNb0.8 M0.2 O4-δ (M=As, Sb, V, and Ta).

LaNb0.8 M0.2 O4-δ (where M=As, Sb, V, and Ta) oxides with pentavalent elements of different ionic sizes were synthesized by a solid-state reaction method. The vibrational properties of these oxides have been investigated. These studies revealed that the substituent element influences both Debye temperature value as well as the Raman active vibrational modes. Additionally, the low-temperature vibrational properties of LaNb0.8 Sb0.2 O4-δ have been determined to show the phase transition occurrence at 260 K which is lower than previously reported.

Boron-doped diamond nanosheet volume-enriched screen-printed carbon electrodes: a platform for electroanalytical and impedimetric biosensor applications.

This paper focuses on the development of a novel electrode based on boron-doped diamond nanosheet full-volume-enriched screen-printed carbon electrodes (BDDPE) for use as an impedimetric biosensor. Impedimetric biosensors offer high sensitivity and selectivity for virus detection, but their use as point-of-care devices is limited by the complexity of nanomaterials' architecture and the receptor immobilisation procedures. The study presents a two-step modification process involving the electroreduction of diazonium salt at the BDDPE and the immobilisation of antibodies using zero-length cross-linkers for a selective impedimetric biosensor of Haemophilus influenzae (Hi). The incorporation of diamond nanosheets into BDDPE leads to enhanced charge transfer and electrochemical behaviour, demonstrating greatly improved electrochemically active surface area compared with unmodified screen-printed electrodes (by 44% and 10% on average for [Ru(NH3)6]Cl2 and K3[Fe(CN)6], respectively). The presented sensing system shows high specificity towards protein D in Hi bacteria, as confirmed by negative controls against potential interference from other pathogens, with an estimated tolerance limit for interference under 12%. The Hi limit of detection by electrochemical impedance spectroscopy was 1 CFU/mL (measured at - 0.13 V vs BDDPE pseudo-reference), which was achieved in under 10 min, including 5 min sample incubation in the presence of the analyte.

Influence of B/N co-doping on electrical and photoluminescence properties of CVD grown homoepitaxial diamond films.

Boron doped diamond (BDD) has great potential in electrical, and electrochemical sensing applications. The growth parameters, substrates, and synthesis method play a vital role in the preparation of semiconducting BDD to metallic BDD. Doping of other elements along with boron (B) into diamond demonstrated improved efficacy of B doping and exceptional properties. In the present study, B and nitrogen (N) co-doped diamond has been synthesized on single crystalline diamond (SCD) IIa and SCD Ib substrates in a microwave plasma-assisted chemical vapor deposition process. The B/N co-doping into CVD diamond has been conducted at constant N flow of N/C âˆ¼ 0.02 with three different B/C doping concentrations of B/C âˆ¼ 2500 ppm, 5000 ppm, 7500 ppm. Atomic force microscopy topography depicted the flat and smooth surface with low surface roughness for low B doping, whereas surface features like hillock structures and un-epitaxial diamond crystals with high surface roughness were observed for high B doping concentrations. KPFM measurements revealed that the work function (4.74-4.94 eV) has not varied significantly for CVD diamond synthesized with different B/C concentrations. Raman spectroscopy measurements described the growth of high-quality diamond and photoluminescence studies revealed the formation of high-density nitrogen-vacancy centers in CVD diamond layers. X-ray photoelectron spectroscopy results confirmed the successful B doping and the increase in N doping with B doping concentration. The room temperature electrical resistance measurements of CVD diamond layers (B/C âˆ¼ 7500 ppm) have shown the low resistance value âˆ¼9.29 Ω for CVD diamond/SCD IIa, and the resistance value âˆ¼16.55 Ω for CVD diamond/SCD Ib samples.

The effect of sunlight and UV lamp exposure on EPR signals in X-ray irradiated touch screens of mobile phones.

Electron paramagnetic resonance (EPR) signals generated by ionizing radiation in touch-screen glasses have been reported as useful for personal dosimetry in people accidently exposed to ionizing radiation. This article describes the effect of light exposure on EPR spectra of various glasses obtained from mobile phones. This effect can lead to significant inaccuracy of the radiation doses reconstructed by EPR. The EPR signals from samples unexposed and exposed to X-rays and/or to natural and artificial light were numerically separated into three model spectra: those due to background (BG), radiation-induced signal (RIS), and light-induced signal (LIS). Although prolonged exposures of mobile phones to UV light are rather implausible, the article indicates errors underestimating the actual radiation doses in dose reconstruction in glasses exposed to UV light even for low fluences equivalent to several minutes of sunshine, if one neglects the effects of light in applied dosimetric procedures. About 5 min of exposure to sunlight or to light from common UV lamps reduced the intensity of the dosimetric spectral components by 20-60% as compared to non-illuminated samples. This effect strongly limits the achievable accuracy of retrospective dosimetry using EPR in glasses from mobile phones, unless their exposure to light containing a UV component can be excluded or the light-induced reduction in intensity of the RIS can be quantitatively estimated. A method for determination of a correction factor accounting for the perturbing light effects is proposed on basis of the determined relation between the dosimetric signal and intensity of the light-induced signal.

The effect of sunlight and UV lamps on EPR signal in nails.

The effects of illumination of nail clippings by direct sunlight, UV lamps and fluorescent bulbs on native and radiation-induced electron paramagnetic resonance (EPR) signals in nails are presented. It is shown that a few minutes of exposure of the nail clippings to light including a UV component (sunlight and UV lamps) generates a strong EPR signal similar to the other EPR signals observable in nails: native background (BKG), mechanically induced (MIS) or radiation-induced (RIS). This effect was observed in clippings exposed and unexposed to ionizing radiation prior to the light illuminations. An exposure of the clippings to fluorescent light without a UV component generated, within the examined range of the light fluences (up to 240 kJ/m2), an EPR signal with considerably lower yield than UV light. The light-induced signal (LIS) decayed after 10 min of water treatment of the samples. In contrast, it was still observable 3 months after illumination in samples stored in air at room temperature, and 3 weeks in frozen samples, respectively. It is concluded that the LIS can considerably affect assessment of the dosimetric RIS components in irradiated nails, and of the background signals in unirradiated nails, thus contributing to errors in EPR dosimetry in nails.

Detection of the Plant Pathogen Pseudomonas Syringae pv. Lachrymans on Antibody-Modified Gold Electrodes by Electrochemical Impedance Spectroscopy.

The present work describes an impedimetric immunosensor for Pseudomonas syringae pv. lachrymans (Psl) detection. This pathogen infects many crop species causing considerable yield losses, thus fast and cheap detection method is in high demand. In the assay, the gold disc electrode was modified with 4-aminothiophenol (4-ATP), glutaraldehyde (GA), and anti-Psl antibodies, and free-sites were blocked with bovine serum albumin (BSA). Sensor development was characterized by cyclic voltammetry (CV) and antigen detection by electrochemical impedance spectroscopy (EIS) measurements. Seven analyzed strains of Psl were verified as positive by the reference method (PCR) and this immunoassay, proving sensor specificity. Label-free electrochemical detection was in the linear range 1 × 103-1.2 × 105 CFU/mL (colony-forming unit) with an R2 coefficient of 0.992 and a detection limit (LOD) of 337 CFU/mL. The sensor did not interfere with negative probes like buffers and other bacteria. The assay was proven to be fast (10 min detection) and easy in preparation. The advantage was the simplicity and availability of the verified analyte (whole bacteria) as the method does not require sample pretreatment (e.g., DNA isolation). EIS biosensing technique was chosen as one of the simplest and most sensitive with the least destructive influence on the probes compared to other electrochemical methods.

Laser-Treated MXene as an Electrochemical Agent to Boost Properties of Semitransparent Photoelectrode Based on Titania Nanotubes.

In this study, Ti3C2Tx underwent laser treatment to reshape it, resulting in the formation of a TiO2/Ti3C2Tx heterojunction. The interaction with laser light induced the formation of spherical TiO2 composed of an anatase-rutile phase on the Ti3C2Tx surface. Such a heterostructure was loaded over a titania nanotube (TNT) layer, and the surface area was enhanced through immersion in a TiCl4 solution followed by thermal treatment. Consequently, the photon-to-electron conversion efficiency exhibits a 10-fold increase as compared to bare TNT. Moreover, for the sample produced with optimized conditions, five times higher photoactivity is observed in comparison to bare TNT. It was shown that under visible light irradiation the most photoactive heterojunction based on the tubular layer reveals a substantial drop in the charge transfer resistance of about 32% with respect to the dark condition. This can be attributed to the narrower band gaps of the modified material and improvement of the separation efficiency of the photogenerated electron-hole pairs. Overall results suggest that this investigation underscores TiO2/Ti3C2Tx as a promising noble-metal-free material that enhances both the electrochemical and photoelectrochemical performances of electrode materials based on TNT that can be further used in light-harvesting applications.

Optimizing Ni-Cr patterned boron-doped diamond band electrodes: Doping effects on electrochemical efficiency and posaconazole sensing performance.

There is growing interest in developing diamond electrodes with defined geometries such as, for example, micrometer-sized electrode arrays to acquire signals for electroanalysis. For electroanalytical sensing applications, it is essential to achieve precise conductive patterns on the insulating surface. This work provides a novel approach to boron-doped diamond patterning using nichrome masking for selective seeding on an oxidized silicon substrate. The optimized process involves nichrome deposition, sonication, chemical etching, seeding, and tailored chemical vapor deposition of boron-doped diamond with an intrinsic layer to suppress boron diffusion. Through a systematic investigation, it was determined that isolated boron-doped diamond band electrodes can be efficiently produced on non-conductive silica. Additionally, the influence of boron doping on electrochemical performance was studied, with higher doping enhancing the electrochemical response of band electrodes. To demonstrate sensing capabilities, boron-doped diamond bands were used to detect posaconazole, an antifungal drug, exploiting its electroactive behaviour. A linear correlation between posaconazole concentration and oxidation peak current was observed over 1.43 × 10-8 - 5.71 × 10-6 M with a 1.4 × 10-8 M detection limit. The developed boron-doped diamond microbands could significantly impact the field of electroanalysis, facilitating detection of diverse biologically relevant molecules. Overall, this diamond patterning approach overcomes major challenges towards all-diamond electrochemical sensor chips.

Enhancing colloidal stability of nanodiamond via surface modification with dendritic molecules for optical sensing in physiological environments.

Pre-treatment of diamond surface in low-temperature plasma for oxygenation and in acids for carboxylation was hypothesized to promote the branching density of the hyperbranched glycidol polymer. This was expected to increase the homogeneity of the branching level and suppress interactions with proteins. As a result, composite nanodiamonds with reduced hydrodynamic diameters that are maintained in physiological environments were anticipated. Surfaces of 140-nm-sized nanodiamonds were functionalized with oxygen and carboxyl groups for grafting of hyperbranched dendritic polyglycerol via anionic ring-opening polymerization of glycidol. The modification was verified with Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. Dynamic light scattering investigated colloidal stability in pH-diverse (2-12) solutions, concentrated phosphate-buffered saline, and cell culture media. Thermogravimetric analysis of nanodiamonds-protein incubations examined non-specific binding. Fluorescence emission was tested across pH conditions. Molecular dynamics simulations modeled interparticle interactions in ionic solutions. The hyperbranched polyglycerol grafting increased colloidal stability of nanodiamonds across diverse pH, high ionic media like 10 × concentrated phosphate-buffered saline, and physiological media like serum and cell culture medium. The hyperbranched polyglycerol suppressed non-specific protein adsorption while maintaining intensive fluorescence of nanodiamonds regardless of pH. Molecular modelling indicated reduced interparticle interactions in ionic solutions correlating with the improved colloidal stability.

Spin-Resolved Band Structure of Hoffman Clathrate [Fe(pz)2Pt(CN)4] as an Essential Tool to Predict Optical Spectra of Metal-Organic Frameworks.

Paramount spin-crossover properties of the 3D-Hoffman metalorganic framework (MOF) [Fe(pz)2Pt(CN)4] are generally described on the basis of the ligand field theory, which provides adequate insight into theoretical and simulation analysis of spintronic complexes. However, the ligand field approximation does not take into account the 3D periodicity of the actual complex lattice and surface effects and therefore cannot predict a full-scale periodic structure without utilizing more advanced methods. Therefore, in this paper, the electronic properties of the exemplar MOF were analyzed from the band structure perspective in low-spin (LS) and high-spin (HS) states. The density-of-states spectra determined for both spin-up and spin-down electrons of Fe d6 orbitals indicate spin-orbital splitting and delocalization for HS due to spin polarization in the iron atom ligand field. Presence of the surface states in the real crystal causes a red shift of the metal-metal charge transfer (MMCT) and metal-ligand charge transfer (MLCT) peaks for both HS and LS states. The addition of residual water molecules and disorder among the pyrazine rings reveal additional influences on the positions of the pyrazine band and, therefore, on the absorption spectra of the crystal. The results show a magnification of the peak correlated with the MLCT in the HS state and a significant red shift of the LS characteristic absorption band. The presented approach involving band structure analysis delivers a more complete image of the electronic properties of the [Fe(pz)2Pt(CN)4] crystalline network and can be a landmark for insightful studies of other MOFs.

Controlling crystallites orientation and facet exposure for enhanced electrochemical properties of polycrystalline MoO3 films.

This study focuses on the development and optimization of MoO3 films on commercially available FTO substrates using the pulsed laser deposition (PLD) technique. By carefully selecting deposition conditions and implementing post-treatment procedures, precise control over crystallite orientation relative to the substrate is achieved. Deposition at 450 °C in O2 atmosphere results in random crystallite arrangement, while introducing argon instead of oxygen to the PLD chamber during the initial stage of sputtering exposes the (102) and (011) facets. On the other hand, room temperature deposition leads to the formation of amorphous film, but after appropriate post-annealing treatment, the (00k) facets were exposed. The deposited films are studied using SEM and XRD techniques. Moreover, electrochemical properties of FTO/MoO3 electrodes immersed in 1 M AlCl3 aqueous solution are evaluated using cyclic voltammetry and electrochemical impedance spectroscopy. The results demonstrate that different electrochemical processes are promoted based on the orientation of crystallites. When the (102) and (011) facets are exposed, the Al3+ ions intercalation induced by polarization is facilitated, while the (00k) planes exposure leads to the diminished hydrogen evolution reaction overpotential.

Fluorescence of nanodiamond cocktails: pH-induced effects through interactions with comestible liquids.

Fluorescent nanodiamonds with nitrogen-vacancy centers have become important nanoscale probes for sensing and imaging. The surface chemistry of the nanodiamonds influences their emission, interactions, and quantum properties. In this work, we propose to utilize fluorescent nanodiamonds as photostable markers for investigation of comestible liquids. We prepared nanodiamond/comestibles suspensions/cocktails with a wide range of pH levels and studied the samples via fluorescence, wettability, and zeta potential. The composition of the created cocktails revealed a strong impact on the properties of the nanodiamond and its surface chemistry, mainly induced by pH but also tuned by specific quenching compounds. Moreover, the stability of the nanodiamonds in the cocktail media was studied, along with various nature-originated compounds influencing their surface termination, polarity, and charge states. Thanks to the stability and biocompatibility of the nanodiamond, it can be applied in monitoring the condition of foodstuffs, and in the detection of toxins and pathogens in them.

Wide-field magnetometry using nitrogen-vacancy color centers with randomly oriented micro-diamonds.

Magnetometry with nitrogen-vacancy (NV) color centers in diamond has gained significant interest among researchers in recent years. Absolute knowledge of the three-dimensional orientation of the magnetic field is necessary for many applications. Conventional magnetometry measurements are usually performed with NV ensembles in a bulk diamond with a thin NV layer or a scanning probe in the form of a diamond tip, which requires a smooth sample surface and proximity of the probing device, often limiting the sensing capabilities. Our approach is to use micro- and nano-diamonds for wide-field detection and mapping of the magnetic field. In this study, we show that NV color centers in randomly oriented submicrometer-sized diamond powder deposited in a thin layer on a planar surface can be used to detect the magnetic field. Our work can be extended to irregular surfaces, which shows a promising path for nanodiamond-based photonic sensors.

Tailoring of Optical Properties of Methacrylate Resins Enriched by HPHT Microdiamond Particles.

Diamond particles have great potential to enhance the mechanical, optical, and thermal properties of diamond-polymer composites. However, the improved properties of diamond-polymer composites depend on the size, dispersibility, and concentration of diamond particles. In the present study, diamond-polymer composites were prepared by adding the microdiamond particles (MDPs) with different concentrations (0.2-1 wt.%) into polymers (acrylate resins) and then subjected to a photocuring process. The surface morphology and topography of the MDPs-polymer composites demonstrated a uniform high-density distribution of MDPs for one wt.% MPDs. Thermogravimetric analysis was employed to investigate the thermal stability of the MDPs-polymer composites. The addition of MDPs has significantly influenced the polymers' thermal degradation. Absorption and emission spectra of thin layers were recorded through UV/Vis spectrophotometry and spectrofluorimetry. The obtained results revealed a significant increase in the fluorescence intensity of MDPs-polymer composites (at 1 wt.% of MDPs, a 1.5×, 2×, and 5× increase in fluorescence was observed for MDPs-green, MDPs-amber daylight, and MDPs-red resin, respectively) compared with the reference polymer resins. The obtained results of this work show the new pathways in producing effective and active 3D-printed optical elements.

Pilot-Scale Studies of WO3/S-Doped g-C3N4 Heterojunction toward Photocatalytic NOx Removal.

Due to the rising concentration of toxic nitrogen oxides (NOx) in the air, effective methods of NOx removal have been extensively studied recently. In the present study, the first developed WO3/S-doped g-C3N4 nanocomposite was synthesized using a facile method to remove NOx in air efficiently. The photocatalytic tests performed in a newly designed continuous-flow photoreactor with an LED array and online monitored NO2 and NO system allowed the investigation of photocatalyst layers at the pilot scale. The WO3/S-doped-g-C3N4 nanocomposite, as well as single components, were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller surface area analysis (BET), X-ray fluorescence spectroscopy (XRF), X-ray photoemission spectroscopy method (XPS), UV-vis diffuse reflectance spectroscopy (DR/UV-vis), and photoluminescence spectroscopy with charge carriers' lifetime measurements. All materials exhibited high efficiency in photocatalytic NO2 conversion, and 100% was reached in less than 5 min of illumination under simulated solar light. The effect of process parameters in the experimental setup together with WO3/S-doped g-C3N4 photocatalysts was studied in detail. Finally, the stability of the composite was tested in five subsequent cycles of photocatalytic degradation. The WO3/S-doped g-C3N4 was stable in time and did not undergo deactivation due to the blocking of active sites on the photocatalyst's surface.

Rubrene Thin Films with Viably Enhanced Charge Transport Fabricated by Cryo-Matrix-Assisted Laser Evaporation.

Among organic semiconductors, rubrene (RB; C42H28) is of rapidly growing interest for the development of organic and hybrid electronics due to exceptionally long spin diffusion length and carrier mobility up to 20 cm2V-1s-1 in single crystals. However, the fabrication of RB thin films resembling properties of the bulk remains challenging, mainly because of the RB molecule's twisted conformation. This hinders the formation of orthorhombic crystals with strong π-π interactions that support the band transport. In this work, RB films with a high crystalline content were fabricated by matrix-assisted laser evaporation and the associated structure, composition, and transport properties are investigated. Enhanced charge transport is ascribed to the crystalline content of the film. Spherulitic structures are observed on top of an amorphous RB layer formed in the initial deposition stage. In spherulites, orthorhombic crystals dominate, as confirmed by X-ray diffraction and the absorption and Raman spectra. Surprisingly, nanowires several microns in length are also detected. The desorption/ionization mass and X-ray photoelectron spectra consistently show minimal material decomposition and absence of RB peroxides. The observed carrier mobility up to 0.13 cm2V-1s-1, is close to the technologically accepted level, making these rubrene films attractive for spintronic and optoelectronic applications.

Hydrothermal Cobalt Doping of Titanium Dioxide Nanotubes towards Photoanode Activity Enhancement.

Doping and modification of TiO2 nanotubes were carried out using the hydrothermal method. The introduction of small amounts of cobalt (0.1 at %) into the structure of anatase caused an increase in the absorption of light in the visible spectrum, changes in the position of the flat band potential, a decrease in the threshold potential of water oxidation in the dark, and a significant increase in the anode photocurrent. The material was characterized by the SEM, EDX, and XRD methods, Raman spectroscopy, XPS, and UV-Vis reflectance measurements. Electrochemical measurement was used along with a number of electrochemical methods: chronoamperometry, electrochemical impedance spectroscopy, cyclic voltammetry, and linear sweep voltammetry in dark conditions and under solar light illumination. Improved photoelectrocatalytic activity of cobalt-doped TiO2 nanotubes is achieved mainly due to its regular nanostructure and real surface area increase, as well as improved visible light absorption for an appropriate dopant concentration.

Carbon nanoarchitectures as high-performance electrodes for the electrochemical oxidation of landfill leachate.

Nanomaterials and assemblies of the aforementioned into complex architectures constitute an opportunity to design efficient and selective solutions to widespread and emerging environmental issues. The limited disposal of organic matter in modern landfills generates extremely concentrated leachates characterised by high concentrations of refractory compounds. Conventional biochemical treatment methods are unsuitable, while advanced treatment, such coagulation, reverse osmosis and ultrafiltration can be very costly and generate additional waste. Electrochemical oxidation is an established technique to efficiently mineralise a plethora of recalcitrant pollutants, however the selectivity and efficiency of the process are strongly related to the anode material. For this reason, a nanoarchitectured carbon material has been designed and synthesised to improve the capability of the anode towards the adsorption and decomposition of pollutants. Instead of simple nanostructures, intelligently engineered nanomaterials can come in handy for more efficient advanced treatment techniques. In this study, a carbon nanoarchitecture comprising boron-doped vertically aligned graphene walls (BCNWs) were grown on a boron-doped diamond (BDD) interfacial layer. The results show how the peculiar maze-like morphology and the concurrence of different carbon hybridisations resulted in a higher current exchange density. The BDD performed better for the removal of NH4+ while the BCNW-only sample exhibited a faster deactivation. The BDD/BCNW nanoarchitecture resulted in an enhanced COD removal and a NH4+ removal similar to that of BDD, without the intermediate production of NO2- and NO3-.

Thin Films of Nanocrystalline Fe(pz)[Pt(CN)4] Deposited by Resonant Matrix-Assisted Pulsed Laser Evaporation.

Prior studies of the thin film deposition of the metal-organic compound of Fe(pz)Pt[CN]4 (pz = pyrazine) using the matrix-assisted pulsed laser evaporation (MAPLE) method, provided evidence for laser-induced decomposition of the molecular structure resulting in a significant downshift of the spin transition temperature. In this work we report new results obtained with a tunable pulsed laser, adjusted to water resonance absorption band with a maximum at 3080 nm, instead of 1064 nm laser, to overcome limitations related to laser-target interactions. Using this approach, we obtain uniform and functional thin films of Fe(pz)Pt[CN]4 nanoparticles with an average thickness of 135 nm on Si and/or glass substrates. X-ray diffraction measurements show the crystalline structure of the film identical to that of the reference material. The temperature-dependent Raman spectroscopy indicates the spin transition in the temperature range of 275 to 290 K with 15 ± 3 K hysteresis. This result is confirmed by UV-Vis spectroscopy revealing an absorption band shift from 492 to 550 nm related to metal-to-ligand-charge-transfer (MLCT) for high and low spin states, respectively. Spin crossover is also observed with X-ray absorption spectroscopy, but due to soft X-ray-induced excited spin state trapping (SOXIESST) the transition is not complete and shifted towards lower temperatures.