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In our experimental setup (Fig. 1a), the valence electronic structure of Fe[(CO).sub.5] is probed with femtosecond-resolution resonant inelastic X-ray scattering (RIXS) at the Fe [L.sub.3]-edge (Fe [L.sub.3]-RIXS, illustrated in Fig. [...], Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion (1,2). Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site (3-11) that need to be controlled to optimize complexes for photocatalytic hydrogen production (8) and selective carbon-hydrogen bond activation (9-11). An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe[(CO).sub.5] in solution, that the photo-induced removal of CO generates the 16-electron Fe[(CO).sub.4] species, a homogeneous catalyst (12,13) with an electron deficiency at the Fe centre (14,15), in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe[(CO).sub.5] (refs 4, 16-20), was made possible by the ability of femto-second X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.

We determine the pathways in the photo-dissociation reactions of Fe(CO)5 both in the gas phase and in solution by mapping the valence electronic structure of the reaction intermediates with femtosecond X-ray laser spectroscopy.

X-ray diffraction and optical spectroscopic methods is used to investigate the photoinduced structural variations in single crystals of 2,4-dichloro-trans-cinnamic acid. The result observed is unexpected and emphasizes the still-existing problem of predicting changes or remaining of periodicity during chemical reactions in the solid state.

The photophysics of 3,3'-diethylthiacarbocyanine iodide (DTCI) in liquid mixtures of dimethyl sulfoxide (DMSO) with toluene is studied by means of steady-state and time-resolved optical spectroscopy. The findings are explained in terms of the Rulliere model by assuming a fast equilibrium between electronically excited trans and cis isomers of DTCI.

Experimental and theoretical examinations of the spectroscopic properties have been carried out on three charge-transfer model system, covalently linked donor-acceptor compounds of the type pyrene and derivatives of N, N -- dimethylaniline (dimethyl(4-pyren-1-ylphenyl)amine (PyDMA), dimethyl(3-methyl-4-pyren-1-ylphenyl)amine (PyMDMA) and (3,5-dimethyl-4-pyren-1-ylphenyl)deimethylamine (PyDMDMA)). The experiments are interpreted within a statistical framework to determine the results.

We utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO)5 in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO)4 which are observed following a charge transfer photoexcitation of Fe(CO)5 as reported in our previous study [Wernet et al., Nature 520, 78 (2015)]. We find that branching of the reaction pathway likely happens in the 1A1 state of Fe(CO)4. A sub-picosecond time constant of the spin crossover from 1B2 to 3B2 is rationalized by the proposed 1B2 → 1A1 → 3B2 mechanism. Ultrafast ligation of the 1B2 Fe(CO)4 state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the 3B2 Fe(CO)4 ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via 1B2 → 1A1 → 1A0 Fe(CO)4EtOH pathway and the time scale of the 1A1 Fe(CO)4 state ligation is governed by the solute-solvent collision frequency. Our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution. [ABSTRACT FROM AUTHOR]

We present a newly designed compact grating spectrometer for the energy range from 210 eV to 1250 eV, which would include the Kα1,2 emission lines of vital elements like C, N, and O. The spectrometer is based on a grazing incidence spherical varied line spacing grating with 2400 l/mm at its center and a radius of curvature of 58 542 mm. First, results show a resolving power of around 1000 at an energy of 550 eV and a working spectrometer for high vacuum (10-4 mbar) environment without losing photon intensity. [ABSTRACT FROM AUTHOR]

Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion. Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site that need to be controlled to optimize complexes for photocatalytic hydrogen production and selective carbon-hydrogen bond activation. An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)5 in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)4 species, a homogeneous catalyst with an electron deficiency at the Fe centre, in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)5 (refs 4, 16,17,18,19 and 20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes. [ABSTRACT FROM AUTHOR]

We present a table-top soft-x-ray spectrometer for the wavelength range λ = 1-5 nm based on a stable laser-driven x-ray source, making use of a gas-puff target. With this setup, optical light-pump/soft-x-ray probe near-edge x-ray absorption fine structure (NEXAFS) experiments with a temporal resolution of about 230 ps are feasible. Pump-probe NEXAFS measurements were carried out in the 'water-window' region (2.28 nm-4.36 nm) on the manganite Pr0.7Ca0.3MnO3, investigating diminutive changes of the oxygen K edge that derive from an optically induced phase transition. The results show the practicability of the table-top soft-x-ray spectrometer on demanding investigations so far exclusively conducted at synchrotron radiation sources. [ABSTRACT FROM AUTHOR]

In this paper we present a development of a multipurpose vacuum chamber which primal function is to be used in pump/probe experiments with free electron laser (FEL) radiation. The chamber is constructed for serial diffraction and serial spectroscopy allowing a fast exchange of samples during the measurement process. For the fast exchange of samples, liquid jet systems are used. Both applications, utilizing soft x-ray FEL pulses as pump and optical laser pulses as probe and vice versa are documented. Experiments with solid samples as well as the liquid jet samples are presented. When working with liquid jets, a system of automatically refilled liquid traps for capturing liquids has been developed in order to ensure stable vacuum conditions. Differential pumping stages are placed in between the FEL beamline and the experimental chamber so that working pressure in the chamber can be up to four orders of magnitude higher than the pressure in the FEL beamline. [ABSTRACT FROM AUTHOR]

In time-resolved X-ray diffraction (TR-XRD), two different entities can be investigated as a function of time: the structural response function of a system upon photoexcitation and/or the population changes of short-living intermediates during the time course of a reaction. The time scales of these response functions might vary between hours and picoseconds, depending on the effects measured. By correlating the time evolution of structural changes with varying optical properties, it is possible to derive structure–function relationships in a time-dependent manner. The time-dependence of these relationships and the development of relevant methodologies is a major current interest in our group. Systems under investigation are organic materials with optical functionalities (molecular crystals, electron donor–acceptor systems) and solid state reactions (such as topochemical reactions). [ABSTRACT FROM AUTHOR]

In the next decade the scientific community expects a strong impact in physics, chemistry, biology, material research and life sciences by the availability of high-brilliance X-ray radiation from free-electron laser (FEL) sources. In particular, in the field of ultrafast science these new sources will allow new types of experiments, enabling new phenomena to be discovered. Whereas today ultrafast X-ray diffraction experiments are strongly restricted by the limited X-ray flux of current sources of sub-picosecond X-ray pulses, FELs will provide short pulses of typically 1012 photons with a duration of the order of 100 fs and monochromaticity of 10−3. Here, the feasibility of time-resolved single-shot powder diffraction experiments using these intense pulses, and the requirements of these experiments, are discussed. The detector count rates are estimated for diffraction from a model compound in a wide q-regime under the special consideration of high resolving power. In the case of LCLS radiation parameters, single-shot experiments will be feasible although high-resolution powder diffraction will require a reduction of the intrinsic FEL radiation bandwidth. [ABSTRACT FROM AUTHOR]

A general outline of how to perform a light-excited time-resolved diffraction experiment by applying the optical pump/X-ray probe technique is given. Owing to the difference in penetration depths between the optical light (laser) pump and the X-ray probe, only specific or specially designed crystalline systems can be investigated, so special requirements have to be fulfilled concerning the sample and its compartments. A summary of the experimental conditions of optical pump/X-ray probe experiments is presented, emphasizing why the use of powder diffraction is a useful and necessary X-ray technique for this kind of experiment. The possibilities and bottlenecks of time-resolved X-ray diffraction on the picosecond time scale will be demonstrated in the powder diffraction studies of N,N-dirnethylaminobenzonitrile and N,N-diisopropylaminobenzonitrile, where the photo-induced structural changes of these molecular organic systems have been studied as a function of time. [ABSTRACT FROM AUTHOR]

It has been proposed that radiation from free electron laser (FEL) at Hamburg (FLASH) can be used for ultrafast time-resolved x-ray diffraction experiments based on the near-infrared (NIR) pump/FEL probe scheme. Here, investigation probing the ultrafast structural dynamics of periodic nano-crystalline organic matter (silver behenate) with such a scheme is reported. Excitation with a femtosecond NIR laser leads to an ultrafast lattice modification which time evolution has been studied through the scattering of vacuum ultraviolet FEL pulses. The found effect last for 6 ps and underpins the possibility for studying nanoperiodic dynamics down to the FEL source time resolution. Furthermore, the possibility of extending the use of silver behenate (AgBh) as a wavelength and temporal calibration tool for experiments with soft x-ray/FEL sources is suggested. [ABSTRACT FROM AUTHOR]

Photoinduced structural variations in single crystals of 2,4-dichloro-trans-cinnamic acid (C9H6Cl2O2, DiClCA) have been investigated using X-ray diffraction (photocrystallography) and optical spectroscopic methods. During UV irradiation, which initiates the irreversible dimerization reaction, a loss of the long-range order of the reactant single crystal was found, i.e., that the dimerization is a heterogeneous one. This unexpected result emphasizes the still-existing problem of predicting changes or of remaining periodicity during chemical reactions in the solid state. On the basis of the experimental results, we propose a qualitative kinetic reaction scheme for DiClCA heterogeneous dimerization reaction. [ABSTRACT FROM AUTHOR]

The article offers the authors comment on the article "State-Dependent Electron Delocalization Dynamics at the Solute-Solvent Interface: Soft-X-ray Absorption Spectroscopy and Ab Initio Calculations" by S. I. Bokarev and colleagues. The authors are critical on the findings of the study which show the relationship between state-dependent fluorescence yield and electron delocalization based on electron excitation. They also state that the study authors did not sufficiently supported their claims.

Two Co(II) mixed-ligand metal-organic frameworks (MOFs) based on 2-methylimidazole and trimesate were synthesised at room temperature. The structure and properties of the two MOFs, named material Deutsches Elektronen Synchrotron-1 and -2 (mDESY-1 and mDESY-2), were verified by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), SQUID magnetic susceptibility and N 2 adsorption. The structural analysis indicates that mDESY-1 is a 3D ionic framework with 2-methyl-1 H -imidazol-3-ium counterions residing in its pores, while mDESY-2 is a 2D neutral framework isostructural to ITH-1, with water as a co-crystallising solvent. PXRD data demonstrates that mDESY-1 exhibits better crystallinity than mDESY-2. Magnetic measurements indicate that both MOFs are paramagnetic with a weak ferromagnetic transition above room temperature. Although both structures suggest the presence of voids, N 2 adsorption data confirms that these voids are not accessible in either MOF. Nevertheless, mDESY-1 was capable of encapsulating azobenzene during synthesis, which was observed via SCXRD. The encapsulated molecules were then slowly released in ethanol, with a release of up to 30 mg of azobenzene per g of MOF in a period of 60 days.

Resonant inelastic X-ray scattering (RIXS) is an ideal X-ray spectroscopy method to push the combination of energy and time resolutions to the Fourier transform ultimate limit, because it is unaffected by the core-hole lifetime energy broadening. Also, in pump-probe experiments the interaction time is made very short by the same core-hole lifetime. RIXS is very photon hungry so it takes great advantage from high-repetition-rate pulsed X-ray sources like the European XFEL. The Heisenberg RIXS instrument is designed for RIXS experiments in the soft X-ray range with energy resolution approaching the Fourier and the Heisenberg limits. It is based on a spherical grating with variable line spacing and a position-sensitive 2D detector. Initially, two gratings were installed to adequately cover the whole photon energy range. With optimized spot size on the sample and small pixel detector the energy resolution can be better than 40 meV (90 meV) at any photon energy below 1000 eV with the high-resolution (high-transmission) grating. At the SCS instrument of the European XFEL the spectrometer can be easily positioned thanks to air pads on a high-quality floor, allowing the scattering angle to be continuously adjusted over the 65-145° range. It can be coupled to two different sample interaction chambers, one for liquid jets and one for solids, each state-of-the-art equipped and compatible for optical laser pumping in collinear geometry. The measured performances, in terms of energy resolution and count rate on the detector, closely match design expectations. The Heisenberg RIXS instrument has been open to public users since the summer of 2022., (open access.)

We present an investigation of the ultrafast dynamics of the polycyclic aromatic hydrocarbon fluorene initiated by an intense femtosecond near-infrared laser pulse (810 nm) and probed by a weak visible pulse (405 nm). Using a multichannel detection scheme (mass spectra, electron and ion velocity-map imaging), we provide a full disentanglement of the complex dynamics of the vibronically excited parent molecule, its excited ionic states, and fragments. We observed various channels resulting from the strong-field ionization regime. In particular, we observed the formation of the unstable tetracation of fluorene, above-threshold ionization features in the photoelectron spectra, and evidence of ubiquitous secondary fragmentation. We produced a global fit of all observed time-dependent photoelectron and photoion channels. This global fit includes four parent ions extracted from the mass spectra, 15 kinetic-energy-resolved ionic fragments extracted from ion velocity map imaging, and five photoelectron channels obtained from electron velocity map imaging. The fit allowed for the extraction of 60 lifetimes of various metastable photoinduced intermediates.

The application of two-photon excitation (TPE) in the study of light-responsive materials holds immense potential due to its deeper penetration and reduced photodamage. Despite these benefits, TPE has been underutilised in the investigation of the photoinduced spin crossover (SCO) phenomenon. Here, we employ TPE to delve into the out-of-equilibrium dynamics of a SCO Fe II dimer of the form [Fe II (HL) 2 ] 2 (BF 4 ) 4 ·2MeCN (HL = 3,5-bis{6-(2,2'-bipyridyl)}pyrazole). Optical transient absorption (OTA) spectroscopy in solution proves that the same dynamics take place under both one-photon excitation (OPE) and TPE. The results show the emergence of the photoinduced high spin state in less than 2 ps and with a lifetime of 147 ns. Time-resolved photocrystallography (TRXRD) reveals a single molecular reorganisation within the first 500 ps following TPE. Additionally, variable temperature single crystal X-ray diffraction (VTSCXRD) and magnetic susceptibility measurements confirm that the thermal transition is silenced by the solvent. While the results of the OTA and TRXRD utilising TPE are intriguing, the high pump fluencies required to excite enough metal centres to the high spin state may impair its practical application. Nonetheless, this study sheds light on the potential of TPE for the investigation of the out-of-equilibrium dynamics of SCO complexes., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Nanostructures formed by the self-assembly of modified/unmodified amino acids have the potential to be useful in several biological/nonbiological applications. In that regard, the greater conformational space provided by γ-amino acids, owing to their additional backbone torsional degrees of freedom and enhanced proteolytic stability, compared to their α-counterparts, should be explored. Though, modified single amino acid-based nanomaterials such as nanobelts or hydrogels are developed by utilizing the monosubstituted γ-amino acids derived from the backbone homologation of phenylalanine (Phe). Examples of a single γ-amino acid-based porous nanostructure capable of accommodating solvent molecules are not really known. The crystal structures of a modified γ 4 (R)Phe residue, Boc-γ 4 (R)Phe-OH, at different temperatures, showed that hydrogen-bonded water molecules are forming a wire inside hydrophilic nanochannels. The dynamics of intermolecular interactions between the water wire and the inner wall of the channel with relation to the temperature change was investigated by analyzing the natural bonding orbital (NBO) calculation results performed with the single crystal structures obtained at different temperature points. The NBO results showed that from 325 K onward, the strength of water-water interactions in the water wire are getting weaker, whereas, for the water-inner wall interactions, it getting stronger, suggesting a favorable change in the orientation of water molecules with temperatures, for the latter., (© 2024. The Author(s).)

The structure of the title salt, C 4 H 7 N 2 + ·C 9 H 5 O 6 - ( 1 ), is reported. The compound is built from a protonated 2-methyl-imidazole and a singly deprotonated trimesic acid. Detailed analysis of bond distances and angles for both ions reveals subtle differences compared with their neutral mol-ecule counterpart. Analysis of the crystal packing in compound 1 reveals the formation of undulating chains by the ions through hydrogen bonding. The chains stack along the b axis through π-π inter-actions and inter-connect with other chains in an out-of-phase arrangement along the ac plane through further hydrogen-bonding inter-actions., (© Baletska et al. 2023.)

Free-electron lasers provide bright, ultrashort, and monochromatic x-ray pulses, enabling novel spectroscopic measurements not only with femtosecond temporal resolution: The high fluence of their x-ray pulses can also easily enter the regime of the non-linear x-ray-matter interaction. Entering this regime necessitates a rigorous analysis and reliable prediction of the relevant non-linear processes for future experiment designs. Here, we show non-linear changes in the L 3 -edge absorption of metallic nickel thin films, measured with fluences up to 60 J/cm 2 . We present a simple but predictive rate model that quantitatively describes spectral changes based on the evolution of electronic populations within the pulse duration. Despite its simplicity, the model reaches good agreement with experimental results over more than three orders of magnitude in fluence, while providing a straightforward understanding of the interplay of physical processes driving the non-linear changes. Our findings provide important insights for the design and evaluation of future high-fluence free-electron laser experiments and contribute to the understanding of non-linear electron dynamics in x-ray absorption processes in solids at the femtosecond timescale., Competing Interests: The authors have no conflicts to disclose., (© 2023 Author(s).)

The structural evolution of spin crossover (SCO) complexes during their spin transition at equilibrium and out-of-equilibrium conditions needs to be understood to enable their successful utilisation in displays, actuators and memory components. In this study, diffraction techniques were employed to study the structural changes accompanying the temperature increase and the light irradiation of a defect [2 × 2] triiron(II) metallogrid of the form [FeII3L H 2 (HL H ) 2 ](BF 4 ) 4 ·4MeCN (FE3), L H = 3,5-bis{6-(2,2'-bipyridyl)}pyrazole. Although a multi-temperature crystallographic investigation on single crystals evidenced that the compound does not exhibit a thermal spin transition, the structural analysis of the defect grid suggests that the flexibility of the grid, provided by a metal-devoid vertex, leads to interesting characteristics that can be used for intermolecular cooperativity in related thermally responsive systems. Time-resolved photocrystallography results reveal that upon excitation with a ps laser pulse, the defect grid shows the first two steps of the out-of-equilibrium process, namely the photoinduced and elastic steps, occurring at the ps and ns time scales, respectively. Similar to a previously reported [2 × 2] tetrairon(II) metallogrid, FE3 exhibits a local distortion of the entire grid during the photoinduced step and a long-range distortion of the lattice during the elastic step. Although the lifetime of the pure photoinduced high spin (HS) state is longer in the tetranuclear grid than in the defect grid, suggesting that the global nuclearity plays a crucial role for the lifetime of the photoinduced species, the influence of the co-crystalising solvent on the lifetime of the photoinduced HS state remains unknown. This study sheds light on the out-of-equilibrium dynamics of a thermally silent defect triiron SCO metallogrid.