Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois, 60439, United States.
Inorg Chem. 2014 Jan 6;53(1):383-92. doi: 10.1021/ic4023294. Epub 2013 Dec 13.
The synthesis, crystal structures, and Raman spectra of seven plutonium chloride compounds are presented. The materials are based upon Pu(VI)O2Cl4(2-) and Pu(IV)Cl6(2-) anions that are charge balanced by protonated pyridinium cations. The single crystal X-ray structures show a variety of donor-acceptor interactions between the plutonium perhalo anions and the cationic pyridine groups. Complementary Raman spectra show that these interactions can be probed through the symmetric vibrational mode of the plutonyl moiety. Unlike previously reported studies in similar uranyl(VI) systems, the facile redox chemistry of plutonium in aqueous solution has demonstrated the feasibility of using not only the An(VI)O2Cl4(2-) anion with approximate D4h symmetry but also the approximately Oh An(IV)Cl6(2-) anion in order to manipulate both the structure and dimensionality of such hybrid materials.
介绍了七种氯化钚化合物的合成、晶体结构和拉曼光谱。这些材料基于 Pu(VI)O2Cl4(2-)和 Pu(IV)Cl6(2-)阴离子，由质子化的吡啶阳离子平衡电荷。单晶 X 射线结构显示了钚过卤阴离子和阳离子吡啶基团之间的各种供体-受体相互作用。补充的拉曼光谱表明，这些相互作用可以通过钚酰基的对称振动模式来探测。与先前在类似铀酰(VI)体系中的报道研究不同，钚在水溶液中的易还原氧化化学性质表明，不仅可以使用具有近似 D4h 对称性的 An(VI)O2Cl4(2-)阴离子，而且可以使用近似 Oh An(IV)Cl6(2-)阴离子来操纵此类混合材料的结构和维度。
