Synthesis of volatile zinc precursors with pyrrolide-Imine ligands

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Polyhedron Pub Date : 2025-03-01 Epub Date: 2025-01-06 DOI:10.1016/j.poly.2024.117386

Ji-Seoung Jeong , Seon Joo Lee , Junseong Lee , Seung Uk Son , Chang Gyoun Kim , Ji Yeon Ryu

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Abstract

Precursors for thin-film deposition have gained increasing research interest, driven by their industrial significance. Herein, we describe the synthesis and characterization of a family of Zn complexes for ZnO fabrication via CVD, ALD/ALE, and MLD. Four zinc complexes possessing pyrrole moieties, Zn(L1)₂ to Zn(L4)₂ (L1H = N-tert-butyl-1-(1H-pyrrol-2-yl)methanimine, L2H = N-tert-pentyl-1-(1H-pyrrol-2-yl)methanimine, L3H = N-neopentyl-1-(1H-pyrrol-2-yl)methanimine, and L4H = N-tert-octyl-1-(1H-pyrrol-2-yl)methanimine), were synthesized and characterized using various analytical methods, including nuclear magnetic resonance (NMR), high-resolution mass spectrometry (HR-MS), and X-ray crystallography. The ligands acted as monoanionic bidentate ligands. Single-crystal X-ray diffraction revealed that complexes 2 and 4 were homoleptic monomeric conformers with distorted tetrahedral geometries, with calculated τ’₄ values of 0.744 and 0.738 for 2 and 4, respectively. Thermogravimetric analysis of all complexes showed a clear, single-step weight loss and exceptional volatility, with low residual masses of 0.35 − 4.41 % at 400 °C. The temperature at which a vapor pressure of 1 Torr was reached and the enthalpies of vaporization were calculated using the Clausius-Clapeyron equation, resulting in values of 148 °C and 105.11 kJ/mol for 2, and 169 °C and 101.31 kJ/mol for 4, respectively.

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吡咯烷-亚胺配体合成挥发性锌前驱体

由于具有重要的工业意义，薄膜沉积前驱体的研究日益受到关注。在此，我们描述了一系列用于CVD， ALD/ALE和MLD制备ZnO的Zn配合物的合成和表征。合成了四种具有吡咯基团的锌配合物Zn(L1)2 ~ Zn(L4)2 （L1H = n -叔丁基-1-（1h -吡咯-2-基）甲亚胺，L2H = n -叔戊基-1-（1h -吡咯-2-基）甲亚胺，L3H = n -新戊基-1-（1h -吡咯-2-基）甲亚胺，L4H = n -叔辛基-1-（1h -吡咯-2-基）甲亚胺），并利用核磁共振（NMR）、高分辨率质谱（HR-MS）和x射线晶体学等分析方法对其进行了表征。配体表现为单阴离子双齿配体。单晶x射线衍射结果表明，配合物2和4是具有畸变四面体形状的异构单体构象，其τ′4值分别为0.744和0.738。所有配合物的热重分析显示出明显的单步失重和异常的挥发性，在400°C时残余质量为0.35 - 4.41%。采用克劳usius- clapeyron方程计算了达到1 Torr蒸汽压时的温度和汽化焓，得到2的值分别为148℃和105.11 kJ/mol， 4的值分别为169℃和101.31 kJ/mol。

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.