Hou Xiaomin, Tang Si-Fu
Shandong Province Key Laboratory of Applied Mycology, College of Life Science, Changcheng Road 700, Chengyang District, Qingdao 266109, China.
College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Changcheng Road 700, Chengyang District, Qingdao 266109, China.
Inorg Chem. 2021 Feb 1;60(3):1869-1876. doi: 10.1021/acs.inorgchem.0c03316. Epub 2021 Jan 20.
A series of ionic uranyl-containing complexes, namely [Cmim][UO(ccnm)] (), [Cmim][UO(ccnm)] (), [N][UO(ccnm)][HO] (), and [P][UO(dcnm)(ccnm)] () [(ccnm) = carbamoylcyanonitrosomethanide; dcnm = dicyanonitrosomethanide; (Cmim) = 1-ethyl-3-methylimidazolium; (Cmim) = 1-butyl-3-methylimidazolium; (N) = tetramethylammonium; (P) = tributyl(ethyl)phosphonium)], were isolated from in situ formed dcnm-based ionic liquids and characterized systematically. It was found that the dcnm anions transformed into ccnm anions during the reactions. These anions coordinate with the uranyl cations in chelate or terminal monodentate coordination mode, affording negative divalent complex anions which can combine with different organic cations and form ionic uranyl-containing complexes. Plenty of C-H···O, N-H···O, C-H···N, N-H···N, and H···H weak interactions are formed in the crystal structures. The transformation of cyano to amide groups contributes to the crystallinity and leads to higher melting points as well as the luminescence quenching of these compounds.
一系列含铀酰离子的配合物，即[Cmim][UO(ccnm)]（）、[Cmim][UO(ccnm)]（）、[N][UO(ccnm)][HO]（）和[P][UO(dcnm)(ccnm)]（）[（ccnm）=氨基甲酰基氰基亚硝基甲烷化物；dcnm =二氰基亚硝基甲烷化物；（Cmim）= 1-乙基-3-甲基咪唑鎓；（Cmim）= 1-丁基-3-甲基咪唑鎓；（N）=四甲基铵；（P）=三丁基（乙基）鏻]，是从原位形成的基于dcnm的离子液体中分离出来的，并进行了系统表征。研究发现，在反应过程中dcnm阴离子转化为ccnm阴离子。这些阴离子以螯合或末端单齿配位模式与铀酰阳离子配位，形成负二价配合物阴离子，该阴离子可与不同的有机阳离子结合并形成含铀酰离子的配合物。在晶体结构中形成了大量的C-H···O、N-H···O、C-H···N、N-H···N和H···H弱相互作用。氰基向酰胺基团的转化有助于结晶度提高，并导致这些化合物具有更高的熔点以及发光猝灭。
