Matched Ligands for Small, Stable Colloidal Nanoparticles of Copper, Cuprous Oxide and Cuprous Sulfide.
Matched Ligands for Small, Stable Colloidal Nanoparticles of Copper, Cuprous Oxide and Cuprous Sulfide.
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用于铜、氧化亚铜和硫化亚铜的小而稳定的胶体纳米颗粒的匹配配体。
DOI：
10.1002/chem.202300228
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Cowie BE
中科院分区：
文献类型：
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作者：
Cowie BE
这项工作适用于铜（0/I）纳米粒子的有机金属路线，并描述了如何匹配配体化学与不同的材料组合物。该合成涉及使有机铜前体均三甲苯基铜（I）[CuMes]z（z=4，5）在低温和有机溶剂中与氢气、空气或硫化氢反应以提供Cu、Cu 2 O或Cu 2S纳米颗粒。使用亚化学计量量的质子化配体（前配体; 0.1-0.2当量vs. [CuMes]z）允许表面配位位点饱和，但避免过量的前配体污染纳米颗粒溶液。 前配体是壬酸（HO 2CR 1）、2-[2-（2-甲氧基乙氧基）乙氧基]乙酸（HO 2CR 2）或二（硫代）壬酸（HS 2CR 1），并且与金属、氧化物或硫化物纳米颗粒匹配。配体交换反应表明，Cu（0）纳米粒子可与羧酸根或二（硫代）羧酸根配位，但Cu 2 O优先与羧酸根配位，Cu 2S优先与二（硫代）羧酸根配位。这项工作突出了有机金属路线的机会，以明确的纳米粒子和需要适当的配体选择。
This work applies organometallic routes to copper(0/I) nanoparticles and describes how to match ligand chemistries with different material compositions. The syntheses involve reacting an organo‐copper precursor, mesitylcopper(I) [CuMes]z(z=4, 5), at low temperatures and in organic solvents, with hydrogen, air or hydrogen sulfide to deliver Cu, Cu2O or Cu2S nanoparticles. Use of sub‐stoichiometric quantities of protonated ligand (pro‐ligand; 0.1–0.2 equivalents vs. [CuMes]z) allows saturation of surface coordination sites but avoids excess pro‐ligand contaminating the nanoparticle solutions. The pro‐ligands are nonanoic acid (HO2CR1), 2‐[2‐(2‐methoxyethoxy)ethoxy]acetic acid (HO2CR2) or di(thio)nonanoic acid, (HS2CR1), and are matched to the metallic, oxide or sulfide nanoparticles. Ligand exchange reactions reveal that copper(0) nanoparticles may be coordinated by carboxylate or di(thio)carboxylate ligands, but Cu2O is preferentially coordinated by carboxylate ligands and Cu2S by di(thio)carboxylate ligands. This work highlights the opportunities for organometallic routes to well‐defined nanoparticles and the need for appropriate ligand selection.