Stalzer Madelyn M, Lohr Tracy L, Marks Tobin J
Department of Chemistry , Northwestern University , Evanston , Illinois 60208 , United States.
Inorg Chem. 2018 Mar 19;57(6):3017-3024. doi: 10.1021/acs.inorgchem.7b02476. Epub 2018 Feb 28.
A series of N, N'-dialkyl-β-diketiminato manganese(II) complexes was synthesized and characterized by single crystal X-ray diffraction, UV-vis and FTIR spectroscopy, and then assayed for volatility, thermal stability, and surface reactivity relevant to vapor-phase film growth processes. Bis( N, N'-dimethyl-4-amino-3-penten-2-imine) manganese(II), 1, and bis( N- N'-diisopropyl-4-amino-3-penten-2-imine) manganese(II), 2, specifically, emerge as the most promising candidates, balancing volatility (sublimation temperatures < 100 °C at 100 mTorr) with coordinative unsaturation and reactivity, as revealed by rapid release of ligand in the presence of a silica surface. Good correlation is observed between buried volume calculations and relative surface reactivity data, indicating that metal availability resulting from sterically open ligand alkyl substituents increases surface reactivity. The thermal stability, volatility, and reactivity exhibited by these compounds render them promising precursors for the growth of manganese oxide films via vapor-phase growth processes.
合成了一系列N,N'-二烷基-β-二酮亚胺基锰(II)配合物,并通过单晶X射线衍射、紫外可见光谱和傅里叶变换红外光谱对其进行了表征,然后对其与气相薄膜生长过程相关的挥发性、热稳定性和表面反应性进行了测定。具体而言,双(N,N'-二甲基-4-氨基-3-戊烯-2-亚胺)锰(II)(1)和双(N,N'-二异丙基-4-氨基-3-戊烯-2-亚胺)锰(II)(2)成为最有前景的候选物,在挥发性(100 mTorr下升华温度<100°C)与配位不饱和性和反应性之间取得了平衡,这一点通过在二氧化硅表面存在时配体的快速释放得以体现。在埋藏体积计算和相对表面反应性数据之间观察到良好的相关性,表明由空间开放的配体烷基取代基导致的金属可利用性增加了表面反应性。这些化合物表现出的热稳定性、挥发性和反应性使其成为通过气相生长过程生长氧化锰薄膜的有前景的前驱体。