Alkyl selenol reactivity with common solvents and ligands: influences on phase control in nanocrystal synthesis
Alkyl selenol reactivity with common solvents and ligands: influences on phase control in nanocrystal synthesis
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DOI：
10.1039/d1nr06282d
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发表时间：
2021-12-06
期刊：
影响因子：
6.7
通讯作者：
Macdonald, Janet E.
中科院分区：
文献类型：
--
作者：
Ho, Eric A.;Peng, Antony R.;Macdonald, Janet E.
本研究通过研究十二烷基硒醇反应物的化学性质如何被配体和溶剂环境所改变，发展了对硒化铜纳米晶体合成中控制相的因素的机械理解。1H-1 NMR和Se-77 NMR用于研究常用溶剂（十八烯和二辛基醚）和配体（油胺、油酸、硬脂胺、硬脂酸和三辛基膦）如何在25 ℃、155 ℃和220 ℃下改变十二烷基硒醇反应物的性质。不饱和度易于硒醇加成，羧酸酯进行硒酯化，胺引起的H2Se气体的释放，和膦形成硒化膦。外源水导致氧化双十二烷基二硒醚。NMR研究相关的相，导致在合成的纳米晶硒化铜，其中berzalianite，umangite或亚稳六方相产生的X-射线衍射确定，根据配体和溶剂的结晶。罕见的六方铜2-xSe相的形成可以被分配到的情况下，包括DD 2Se 2作为一个反应中间体，或强大的L-型连接的胺，这是依赖于烷基链的长度。
This study develops mechanistic understanding of the factors which control the phase in syntheses of copper selenide nanocrystals by investigating how the chemistry of the dodecylselenol reactant is altered by the ligand and solvent environment. H-1 NMR and Se-77 NMR were used to study how commonly used solvents (octadecene and dioctylether) and ligands (oleylamine, oleic acid, stearylamine, stearic acid and trioctyl phosphine) change the nature of the dodecylselenol reactant at 25 degrees C, 155 degrees C and 220 degrees C. Unsaturations were prone to selenol additons, carboxylates underwent selenoesterification, amines caused the release of H2Se gas, and the phosphine formed phosphine selenide. Adventitious water caused oxidation to didodecyldiselenide. NMR studies were correlated with the phases that resulted in syntheses of nanocrystalline copper selenides, in which berzalianite, umangite or a metastable hexagonal phase were produced as identified by X-ray diffraction, depending on the ligand and solvent environemnts. Formation of the rare hexagonal Cu2-xSe phase could be assigned to cases that included DD2Se2 as a reactive intermediate, or strong L-type ligation of amines which was dependant on alkyl chain length.