Sniekers Jeroen, Geysens Pieter, Malaquías João C, Vander Hoogerstraete Tom, Van Meervelt Luc, Fransaer Jan, Binnemans Koen
Department of Chemistry, KU Leuven, Celestijnenlaan 200F, P.O. Box 2404, 3001 Heverlee, Belgium.
Dalton Trans. 2017 Oct 3;46(38):12845-12855. doi: 10.1039/c7dt02604h.
Cobalt(ii)-containing liquid metal salts (LMS) with N-alkylimidazole ligands and bis(trifluoromethanesulfonyl)imide (bistriflimide, TfN) or methanesulfonate (mesylate, OMs) anions were synthesized and characterized. The chain length of the alkyl side chain on the imidazole ligand was varied. All compounds were characterized using CHN analysis, DSC and FTIR measurements. Single-crystal X-ray diffraction measurements were performed on six of the compounds for which single crystals of good quality could be obtained. All cobalt(ii) centers are six-coordinate with the N-alkylimidazole ligands in an octahedral configuration and the anions are non-coordinating. The same coordination environment was observed by EXAFS measurements on cobalt(ii) liquid metal salts in the liquid state. The electrochemical properties of the compounds with the lowest melting temperatures were investigated using cyclic voltammetry. It was found that part of the current was consumed in the electrodeposition of cobalt, whereas the other part of the current was consumed in the electrochemical formation of cobalt(0) nanoparticles.
合成并表征了含有钴(II)的液态金属盐(LMS),其具有N-烷基咪唑配体以及双(三氟甲磺酰)亚胺(双三氟甲磺酰亚胺,TfN)或甲磺酸盐(甲磺酸盐,OMs)阴离子。咪唑配体上烷基侧链的链长有所变化。所有化合物均通过CHN分析、差示扫描量热法(DSC)和傅里叶变换红外光谱(FTIR)测量进行表征。对其中六种能够获得高质量单晶的化合物进行了单晶X射线衍射测量。所有钴(II)中心均为六配位,N-烷基咪唑配体呈八面体构型,且阴离子不参与配位。通过对液态钴(II)液态金属盐进行扩展X射线吸收精细结构(EXAFS)测量也观察到了相同的配位环境。使用循环伏安法研究了熔点最低的化合物的电化学性质。发现部分电流消耗于钴的电沉积,而另一部分电流消耗于钴(0)纳米颗粒的电化学形成。