X-ray radiation damage cycle of solvated inorganic ions.

X-ray-induced damage is one of the key topics in radiation chemistry. Substantial damage is attributed to low-energy electrons and radicals emerging from direct inner-shell photoionization or produced by subsequent processes. We apply multi-electron coincidence spectroscopy to X-ray-irradiated aqueous solutions of inorganic ions to investigate the production of low-energy electrons (LEEs) in a predicted cascade of intermolecular charge- and energy-transfer processes, namely electron-transfer-mediated decay (ETMD) and interatomic/intermolecular Coulombic decay (ICD). An advanced coincidence technique allows us to identify several LEE-producing steps during the decay of 1s vacancies in solvated Mg2+ ions, which escaped observation in previous non-coincident experiments. We provide strong evidence for the predicted recovering of the ion's initial state. In natural environments the recovering of the ion's initial state is expected to cause inorganic ions to be radiation-damage hot spots, repeatedly producing destructive particles under continuous irradiation.

Suppression of X-ray-Induced Radiation Damage to Biomolecules in Aqueous Environments by Immediate Intermolecular Decay of Inner-Shell Vacancies.

The predominant reason for the damaging power of high-energy radiation is multiple ionization of a molecule, either direct or via the decay of highly excited intermediates, as, e.g., in the case of X-ray irradiation. Consequently, the molecule is irreparably damaged by the subsequent fragmentation in a Coulomb explosion. In an aqueous environment, however, it has been observed that irradiated molecules may be saved from fragmentation presumably by charge and energy dissipation mechanisms. Here, we show that the protective effect of the environment sets in even earlier than hitherto expected, namely immediately after single inner-shell ionization. By combining coincidence measurements of the fragmentation of X-ray-irradiated microsolvated pyrimidine molecules with theoretical calculations, we identify direct intermolecular electronic decay as the protective mechanism, outrunning the usually dominant Auger decay. Our results demonstrate that such processes play a key role in charge delocalization and have to be considered in investigations and models on high-energy radiation damage in realistic environments.

Coordination Polymers based on the Neutral Ditopic Ligand (C6H4PO(OCH3)2)2 Involving some f-Block Elements.

An improved synthesis using microwave heating affords (C6H4PO(OCH3)2)2 in excellent isolated yield (95 %). The ligand properties of this bisphosphonateester were explored towards hard metal centers M2+ (M = Ca, UO2) and M3+ (M = La, Ce, Sm, Eu) resulting in coordination polymers, for which the reduction of ionic size of the central metal atom resulted in lower-dimensional structural motifs as opposed to higher dimensional networks obtained for the larger ions. All coordination polymers were characterized by single-crystal X-ray diffraction, IR spectroscopy, and combustion analysis. The ligand was furthermore characterized with multinuclear NMR spectroscopy.