Single Crystal Synthesis Methods Dedicated to Structural Investigations of Very Low Solubility Mixed-Actinide Oxalate Coordination Polymers

• Published in: Crystal growth & design Vol. 12; no. 11; pp. 5447 - 5455
• Main Authors: Tamain, Christelle, Arab-Chapelet, Bénédicte, Rivenet, Murielle, Abraham, Francis, Grandjean, Stéphane
• Format: Journal Article
• Language: English
• Published: Washington,DC American Chemical Society 07.11.2012
• Subjects: Chemical Sciences; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Discharges for spectral sources (including inductively coupled plasmas); Electric discharges; Equations of state, phase equilibria, and phase transitions; Exact sciences and technology; Materials science; Methods of crystal growth; physics of crystal growth; Organic compounds; Physics; Physics of gases, plasmas and electric discharges; Physics of plasmas and electric discharges; Solubility, segregation, and mixing; phase separation; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Metal organic framework; Crystal growth; Crystal form; Molecular structure; Polychelate; Solubility; XRD; Dispersive spectrometry; Crystal growth methods; AES; Monocrystals; Inductively coupled plasma; Valence; Ionization; Rare earths; Americium; Oxalates; Crystal structure
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/cg301039m

Two crystal growth methods dedicated to very low solubility actinide coordination polymers have been developed and applied to the synthesis of mixed actinide(IV)–actinide(IV) or actinide(IV)–actinide(III) oxalate single crystals of a size (typically 100–300 μm) suitable for isolating them and examining their crystal structure. These methods have been optimized on mixed systems composed of U(IV) and lanthanide (surrogate of trivalent actinides) and then assessed on U(IV)–Am(III), Pu(IV)–Am(III), and U(IV)–Pu(IV) mixtures. Three types of single crystals characterized by different structures have been obtained according to the synthesis and the chemical conditions. This is the first time that these well-known or recently discovered key compounds are formed by crystal growth methods specifically developed for actinide crystal handling (i.e., in glove boxes), thus enabling direct structural studies on transuranium element systems and acquisition of basic data. Characterization by X-ray diffraction, UV–visible solid spectroscopy, thermal ionization mass spectroscopy (TIMS), energy-dispersive X-ray spectroscopy (EDS), and inductively coupled plasma atomic emission spectroscopy (ICP-AES) demonstrates the potentialities and complementarity of the two crystal growth methods for obtaining the targeted mixed oxalates (actinide oxidation state and presence of both metallic ions in the crystal). More generally, this development opens broad prospects for single crystal synthesis of novel actinide organic frameworks and their structural description.