Soft X-ray absorption and fragmentation of tin-oxo cage photoresists.

"Tin-oxo cage" organometallic compounds are considered as photoresists for extreme ultraviolet (EUV) photolithography. To gain insight into their electronic structure and reactivity to ionizing radiation, we trapped bare gas-phase n-butyltin-oxo cage dications [(BuSn)12O14(OH)6]2+ in an ion trap and investigated their fragmentation upon soft X-ray photoabsorption by means of mass spectrometry. In complementary experiments, the tin-oxo cages with hydroxide and trifluoroacetate counter-anions were cast in thin films and studied using X-ray transmission spectroscopy. Quantum-chemical calculations were used to interpret the observed spectra. At the carbon K-edge, a distinct pre-edge absorption band can be attributed to transitions in which electrons are promoted from C1s orbitals to the lowest unoccupied molecular orbitals, which are delocalized orbitals with strong antibonding (Sn-C σ*) character. At higher energies, the most prominent resonant transitions involve C-C and C-H σ* valence states and Rydberg (3s and 3p) states. In the solid state, the onset of continuum ionization is shifted by ∼5 eV to lower energy with respect to the gas phase, due to the electrostatic effect of the counterions. The O K-edge also shows a pre-edge absorption, but it is devoid of any specific features, because there are many transitions from the different O1s orbitals to a large number of vacant orbitals. In the gas phase, formation of the parent [(BuSn)12O14(OH)6]3+ radical ion is not observed at the C K-edge nor at the O K-edge, because the loss of a butyl group from this species is very efficient. We do observe a number of triply charged photofragment ions, some of which have lost up to 5 butyl groups. Structures of these species are proposed based on quantum-chemical calculations, and pathways of formation are discussed. Our results provide insight into the electronic structure of alkyltin-oxo cages, which is a prerequisite for understanding their response to EUV photons and their performance as EUV photoresists.

Soft X-ray signatures of cationic manganese-oxo systems, including a high-spin manganese(V) complex.

Manganese-oxo species catalyze key reactions, including C-H bond activation or dioxygen formation in natural photosynthesis. To better understand relevant reaction intermediates, we characterize electronic states and geometric structures of [MnOn]+ manganese-oxo complexes that represent a wide range of manganese oxidation states. To this end, we apply soft X-ray spectroscopy in a cryogenic ion trap, combined with multiconfigurational wavefunction calculations. We identify [MnO2]+ as a rare high-spin manganese(V) oxo complex with key similarities to six-coordinated manganese(V) oxo systems that are proposed as reaction intermediates in catalytic dioxygen bond formation.

Iron L3-edge energy shifts for the full range of possible 3d occupations within the same oxidation state of iron halides.

Oxidation states are integer in number but dn configurations of transition metal centers vary continuously in polar bonds. We quantify the shifts of the iron L3 excitation energy, within the same formal oxidation state, in a systematic L-edge X-ray absorption spectroscopy study of diatomic gas-phase iron(II) halide cations, [FeX]+,where X = F, Cl, Br, I. These shifts correlate with the electronegativity of the halogen, and are attributed exclusively to a fractional increase in population of 3d-derived orbitals along the series as supported by charge transfer multiplet simulations and density functional theory calculations. We extract an excitation energy shift of 420 meV ± 60 meV spanning the full range of possible 3d occupations between the most ionic bond in [FeF]+ and covalently bonded [FeI]+.

X-ray Induced Fragmentation of Protonated Cystine.

We demonstrate site-specific X-ray induced fragmentation across the sulfur L-edge of protonated cystine, the dimer of the amino acid cysteine. Ion yield NEXAFS were performed in the gas phase using electrospray ionization (ESI) in combination with an ion trap. The interpretation of the sulfur L-edge NEXAFS spectrum is supported by Restricted Open-Shell Configuration Interaction (ROCIS) calculations. The fragmentation pathway of triply charged cystine ions was modeled by Molecular Dynamics (MD) simulations. We have deduced a possible pathway of fragmentation upon excitation and ionization of S 2p electrons. The disulfide bridge breaks for resonant excitation at lower photon energies but remains intact upon higher energy resonant excitation and upon ionization of S 2p. The larger fragments initially formed subsequently break into smaller fragments.

Isolation and Characterization of the Homoleptic Nickel(I) and Nickel(II) Bis-benzene Sandwich Cations.

A stable salt of the metalloradical [Ni(C6 H6 )2 ]+ hitherto unknown in the condensed phase was synthesized from [Ni(CO)4 ]+ [WCA]- and benzene ([WCA]- =[F{Al(ORF )3 }2 ]- ; RF =C(CF3 )3 ). Single crystal XRD reveals a remarkable asymmetrically η3 ,η6 -slipped sandwich structure. The magnetic properties of the [Ni(C6 H6 )2 ]+ cation were determined in solution and in the gas phase. Oxidation with the synergistic Ag+ /0.5 l2 system led to the salt [Ni(C6 H6 )2 ]2+ ([WCA]- )2 . All products were fully characterized by means of IR, Raman, NMR/EPR, single crystal and powder XRD.

Breaking inversion symmetry by protonation: experimental and theoretical NEXAFS study of the diazynium ion, N2H.

As an example of symmetry breaking in NEXAFS spectra of protonated species we present a high resolution NEXAFS spectrum of protonated dinitrogen, the diazynium ion N2H+. By ab initio calculations we show that the spectrum consists of a superposition of two nitrogen 1s absorption spectra, each including a π* band, and a nitrogen 1s to H+ charge transfer band followed by a weak irregular progression of high energy excitations. Calculations also show that, as an effect of symmetry breaking by protonation, the π* transitions are separated by 0.23 eV, only slightly exceeding the difference in the corresponding dark (symmetry forbidden) and bright (symmetry allowed) core excitations of neutral N2. By DFT and calculations and vibrational analysis, the complex π* excitation band of N2H+ is understood as due to the superposition of the significantly different vibrational progressions of excitations from terminal and central nitrogen atoms, both leading to bent final state geometries. We also show computationally that the electronic structure of the charge transfer excitation smoothly depends on the nitrogen-proton distance and that there is a clear extension of the spectra going from infinity to close nitrogen-proton distance where fine structures show some, although not fully detailed, similarities. An interesting feature of partial localization of the nitrogen core orbitals, with a strong, non-monotonous, variation with nitrogen-proton distance could be highlighted. Specific effects could be unraveled when comparing molecular cation NEXAFS spectra, as represented by recently recorded spectra of N2+ and CO+, and spectra of protonated molecules as represented here by the N2H+ ion. Both types containing rich physical effects not represented in NEXAFS of neutral molecules because of the positive charge, whereas protonation also breaks the symmetry. The effect of the protonation on dinitrogen can be separated in charge, which extends the high-energy part of the spectrum, and symmetry-breaking, which is most clearly seen in the low-energy π* transition.

The carbon and oxygen K-edge NEXAFS spectra of CO.

We present and analyze high resolution near edge X-ray absorption fine structure (NEXAFS) spectra of CO+ at the carbon and oxygen K-edges. The spectra show a wealth of features that appear very differently at the two K-edges. The analysis of these features can be divided into three parts; (i) repopulation transition to the open shell orbital - here the C(1s) or O(1s) to 5σ transition, where the normal core hole state is reached from a different initial state and different interaction than in X-ray photoelectron spectroscopy; (ii) spin coupled split valence bands corresponding to C(1s) or O(1s) to π* transitions; (iii) remainder weak and long progressions towards the double ionization potentials containing a manifold of peaks. These parts, none of which has correspondence in NEXAFS spectra of neutral molecules, are dictated by the localization of the singly occupied 5σ orbital, adding a dimension of chemistry to the ionic NEXAFS technique.

Soft X-ray Spectroscopy as a Probe for Gas-Phase Protein Structure: Electron Impact Ionization from Within.

Preservation of protein conformation upon transfer into the gas phase is key for structure determination of free single molecules, for example using X-ray free-electron lasers. In the gas phase, the helicity of melittin decreases strongly as the protein's protonation state increases. We demonstrate the sensitivity of soft X-ray spectroscopy to the gas-phase structure of melittin cations ([melittin+qH]q+ , q=2-4) in a cryogenic linear radiofrequency ion trap. With increasing helicity, we observe a decrease of the dominating carbon 1 s-π* transition in the amide C=O bonds for non-dissociative single ionization and an increase for non-dissociative double ionization. As the underlying mechanism we identify inelastic electron scattering. Using an independent atom model, we show that the more compact nature of the helical protein conformation substantially increases the probability for off-site intramolecular ionization by inelastic Auger electron scattering.

Access to the Bis-benzene Cobalt(I) Sandwich Cation and its Derivatives: Synthons for a "Naked" Cobalt(I) Source?

The synthesis and structural characterization of the hitherto unknown parent Co(bz)2+ (bz=benzene) complex and several of its derivatives are described. Their synthesis starts either from a CoCO5+ salt, or directly from Co2 (CO)8 and a Ag+ salt. Stability and solubility of these complexes was achieved by using the weakly coordinating anions (WCAs) [Al(ORF )4 ]- and [F{Al(ORF )3 }2 ]- {RF =C(CF3 )3 } and the solvent ortho-difluorobenzene (o-DFB). The magnetic properties of Co(bz)2+ were measured and compared in the condensed and gas phases. The weakly bound Co(o-dfb)2+ salts are of particular interest for the preparation of further CoI salts, for example, the structurally characterized low-coordinate 12 valence electron Co(Pt Bu3 )2+ and Co(NHC)2+ salts.

Probing Structural Information of Gas-Phase Peptides by Near-Edge X-ray Absorption Mass Spectrometry.

Near-edge X-ray absorption mass spectrometry (NEXAMS) is an action-spectroscopy technique of growing interest for investigations into the spatial and electronic structure of biomolecules. It has been used successfully to give insights into different aspects of the photodissociation of peptides and to probe the conformation of proteins. It is a current question whether the fragmentation pathways are sensitive toward effects of conformational isomerism, tautomerism, and intramolecular interactions in gas-phase peptides. To address this issue, we studied the cationic fragments of cryogenically cooled gas-phase leucine enkephalin ([LeuEnk+H]+) and methionine enkephalin ([MetEnk+H]+) produced upon soft X-ray photon absorption at the carbon, nitrogen, and oxygen K-edges. The interpretation of the experimental ion yield spectra was supported by density-functional theory and restricted-open-shell configuration interaction with singles (DFT/ROCIS) calculations. The analysis revealed several effects that could not be rationalized based on the peptide's amino acid sequences alone. Clear differences between the partial ion yields measured for both peptides upon C 1s → π*(C═C) excitations in the aromatic amino acid side chains give evidence for a sulfur-aromatic interaction between the methionine and phenylalanine side chain of [MetEnk+H]+. Furthermore, a peak associated with N 1s → π*(C═N) transitions, linked to a tautomeric keto-to-enol conversion of peptide bonds, was only present in the photon energy resolved ion yield spectra of [MetEnk+H]+.

The electronic structure and deexcitation pathways of an isolated metalloporphyrin ion resolved by metal L-edge spectroscopy.

The local electronic structure of the metal-active site and the deexcitation pathways of metalloporphyrins are crucial for numerous applications but difficult to access by commonly employed techniques. Here, we applied near-edge X-ray absorption mass spectrometry and quantum-mechanical restricted active space calculations to investigate the electronic structure of the metal-active site of the isolated cobalt(iii) protoporphyrin IX cation (CoPPIX+) and its deexcitation pathways upon resonant absorption at the cobalt L-edge. The experiments were carried out in the gas phase, thus allowing for control over the chemical state and molecular environment of the metalloporphyrin. The obtained mass spectra reveal that resonant excitations of CoPPIX+ at the cobalt L3-edge lead predominantly to the formation of the intact radical dication and doubly charged fragments through losses of charged and neutral side chains from the macrocycle. The comparison between experiment and theory shows that CoPPIX+ is in a 3A2g triplet ground state and that competing excitations to metal-centred non-bonding and antibonding σ* molecular orbitals lead to distinct deexcitation pathways.

Site-Selective Dissociation upon Sulfur L-Edge X-ray Absorption in a Gas-Phase Protonated Peptide.

Site-selective dissociation induced by core photoexcitation of biomolecules is of key importance for the understanding of radiation damage processes and dynamics and for its promising use as "chemical scissors" in various applications. However, identifying products of site-selective dissociation in large molecules is challenging at the carbon, nitrogen, and oxygen edges because of the high recurrence of these atoms and related chemical groups. In this paper, we present the observation of site-selective dissociation at the sulfur L-edge in the gas-phase peptide methionine enkephalin, which contains only a single sulfur atom. Near-edge X-ray absorption mass spectrometry has revealed that the resonant S 2p → σ*C-S excitation of the sulfur contained in the methionine side chain leads to site-selective dissociation, which is not the case after core ionization above the sulfur L-edge. The prospects of such results for the study of charge dynamics in biomolecular systems are discussed.

Near-Edge Soft X-ray Absorption Mass Spectrometry of Protonated Melittin.

We have investigated the photoionization and photofragmentation yields of gas-phase multiply protonated melittin cations for photon energies at the K-shell absorption edges of carbon, nitrogen, and oxygen. Two similar experimental approaches were employed. In both experiments, mass selected [melittin+qH]q+ (q=2-4) ions were accumulated in radiofrequency ion traps. The trap content was exposed to intense beams of monochromatic soft X-ray photons from synchrotron beamlines and photoproducts were analyzed by means of time-of-flight mass spectrometry. Mass spectra were recorded for fixed photon energies, and partial ion yield spectra were recorded as a function of photon energy. The combination of mass spectrometry and soft X-ray spectroscopy allows for a direct correlation of protein electronic structure with various photoionization channels. Non-dissociative single and double ionization are used as a reference. The contribution of both channels to various backbone scission channels is quantified and related to activation energies and protonation sites. Soft X-ray absorption mass spectrometry combines fast energy deposition with single and double ionization and could complement established activation techniques. Graphical Abstract ᅟ.

Size-Dependent Ligand Quenching of Ferromagnetism in Co3(benzene)n+ Clusters Studied with X-ray Magnetic Circular Dichroism Spectroscopy.

Cobalt-benzene cluster ions of the form Co3(bz)n+ (n = 0-3) were produced in the gas phase, mass-selected, and cooled in a cryogenic ion trap held at 3-4 K. To explore ligand effects on cluster magnetic moments, these species were investigated with X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopy. XMCD spectra yield both the spin and orbital angular momenta of these clusters. Co3+ has a spin magnetic moment of µS = 6 µB and an orbital magnetic moment of µL = 3 µB. Co3(bz)+ and Co3(bz)2+ complexes were found to have spin and orbital magnetic moments identical to the values for ligand-free Co3+. However, coordination of the third benzene to form Co3(bz)3+ completely quenches the high spin state of the system. Density functional theory calculations elucidate the spin states of the Co3(bz)n+ species as a function of the number of attached benzene ligands, explaining the transition from septet to singlet for n = 0 → 3.