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Chimica

半导体回转金属硫框架结晶的硫醇构建块的合成

Published: April 09, 2018
doi:
10.3791/57455
, , ,
1School of Chemical Engineering and Light Industry,Guangdong University of Technology, 2Department of Chemistry,City University of Hong Kong

Summary

在这里, 我们提出了一锅, 过渡无金属合成的硫醇和 thioesters 从芳香卤化物和 thiomethoxide 钠, 其次是制备的单一晶体的金属 dithiolene 网络使用硫醇物种产生的就地从更稳定和易于驾驭的硫酯。

Abstract

我们提出了一种制备硫酯分子的方法, 作为硫醇连接器的掩蔽形式及其在高度有序的单晶态中获取半导体和多孔金属 dithiolene 网络的利用。不同于高度反应自由站立的硫醇, 它倾向于分解和复杂化金属 thiolate 开放框架的结晶, 硫酯反应原位提供硫醇种类, 为缓和之间的反应硫醇单位和金属中心, 从而改善结晶。具体地说, 硫酯是在一锅工序中合成的: 芳香溴 (hexabromotriphenylene) 在剧烈的条件下与过量 thiomethoxide 反应, 首先形成硫醚类中间产物。硫醚类然后 demethylated 过剩的 thiomethoxide 提供 thiolate 负离子, 酰形成硫酯产品。用标准柱层析法对硫酯进行了简便纯化, 然后直接在骨架合成中使用, 其中氢氧化钠和乙二胺用于恢复原位硫酯到硫醇连接器组装单晶 Pb (II)-dithiolene 网络。与其他的硫醇合成方法 (e. g) 相比, 用钠金属和液态氨裂解烷基硫醚类, 这里的硫酯合成使用简单的条件和经济试剂。此外, 硫酯产品稳定, 可以方便地处理和储存。更重要的是, 与访问水晶金属 thiolate 开放框架的一般困难相反, 我们证明使用硫酯进行原位的硫醇连接器的形成大大提高了固态的结晶度. 产品。我们打算通过披露硫酯的合成协议以及水晶骨架固体, 鼓励在技术上重要的金属硫框架方面开展更广泛的研究工作。

Introduction

目前有极大的兴趣使用强, 极化金属硫 (e. g., 金属 thiolate) 链接, 用于构造具有增强电催化和导电性能的开放框架材料1,2,3,4,5,6,7,8,9,10. 除了在延长的状态下促进电子相互作用和运输外, 软和共价键金属硫的连接也给水环境中的应用提供了更好的稳定性。在含硫的积木中, 对称的, 多齿多环芳烃积木, 如 23, 67, 1011-苯并菲 hexathiol (HTT)9,11,12, 13,14不仅提供高度极化的π电子, 而且在框架设计和合成方面也提供了明显的优势。首先, 刚性和对称的苯并菲核心, 结合螯合 dithiolene 组的 HTT, 有助于锁定金属离子在常规的粘合图案, 简化预期网络的结构预测7,15. 与硫磺连接器的刚性和开放几何结合, 具有大量孔隙特征的框架结构通常可以在固态中实现。

在组装硫醇设备金属 orangic 框架 (MOF) 材料的一个主要挑战是植根于有机链接分子的合成。在经典的协议中, 硫醇基团必须是从苯酚组中提取的, 使用纽曼-Kwart 重排O-芳 thiocarbamate 前体16,17,18。然而, 这种方法涉及对苯酚前体分子的精心制备步骤以及高温固相转化的潜在并发症。另一种制造硫醇的方法是在苛刻的条件下使用 thioethers 的还原脱, 例如, 液态氨水中的钠金属 19, 20, 21, 22, 而不是与羧基和其他许多捐助函数兼容, 用于网络建设。

相比之下, 此处提出的协议具有多种优点: 安全性、方便性、成本效益以及与其他功能组 (e. g、carbonitrile 和吡啶) 的兼容性。通过大力加热一般廉价的芳香卤化物 (e. g, hexabromotriphenylene) 和 thiomethoxide 阴离子, thiolate 负离子产生 (通过甲基硫醚类中间产物), 然后酰给稳定和易于处理的硫酯产品-所有在一个锅。

我们还将描述一个程序, 利用硫酯分子作为连接器的蒙面形式, 以获取单一晶体半导体和多孔金属 dithiolene 网络。不同于高度反应自由站立的硫醇, 它倾向于分解和复杂化金属 thiolate 开放框架的结晶, 硫酯可以容易地被切开(e. g, 由氢氧化钠或乙二胺)就地提供硫醇类, 有助于减轻硫醇单位和金属中心之间的反应, 从而改善结晶。

这种制备硫醇/硫酯的议定书尚未被其他群体广泛用于金属-硫框架的新兴领域, 尽管 thiolate 阴离子的烷基芳 thioethers 的亲核 dealkylations 已经被有机化学家23,24,25,26。通过展示这种有效的 thioesters 合成方法及其用于促进金属硫网络的结晶, 我们希望进一步努力弥合合成有机化学与固态化学, 有助于快速、健康地发展多孔骨架。

Protocol

警告: 使用前请查阅所有相关的材料安全数据表。二硫化甲和 thiomethoxide 钠是强烈的恶臭, 应在通风罩中处理。金属钠具有极强的反应性, 对潜在的火灾和爆炸危险需要特别的安全措施。除使用油烟机外, 个人防护设备 (安全眼镜、手套、实验室大衣、全长长裤和闭趾鞋) 应适当采用。以下程序的一部分涉及标准的无空气处理技术。 1. Thiomethoxide 钠的制备 (CH3SNa) ?…

Representative Results

HVaTT 分子的红外光谱 (由 KBr 颗粒法收集) 以其最大吸收率为1700厘米-1, 按照硫酯官能团的羰基拉伸。1HVaTT (400 MHz、CDCl3) 的 H 核磁共振谱显示了δ8.47 中的一个单线, 从芳香氢, 连同 4 multiplets 从脂肪族质子: δ 8.47 (s, 6H, CHAr), 2.75-2.72 (t, J = 7.4, 12H, CH2), 1.81-1. 77 (m,12H, ch2), 1.50-1. 45 (dd, J = 7.4, 12H, CH2), 1.00-0. 97 (t, J</em…

Discussion

溴组与 thiomethoxide 阴离子的反应显然首先产生了甲基硫醚类, 然后 demethylated 过量 thiomethoxide 提供 thiolate 负离子产品。为了确保完全转化为所需的 thiolate 阴离子 (特别是 polybromide 基板如 HBT), 长时间加热的旺盛条件 (例如, 240 °c 超过48小时) 与大量过量钠 thiomethoxide (例如, 超过三倍的摩尔的溴组) 是必不可少的。防止反应物和产物的 thiolate 种类的氧化也需要氮气保护。酰化步骤 (例?…

Divulgazioni

The authors have nothing to disclose.

Acknowledgements

这项工作得到了中国国家自然科学基金 (21471037)、广东省杰出青年学者基金 (15ZK0307)、广东科技规划项目 (2017A050506051) 和香港特区研究资助委员会 [GRF 11303414]。

Materials

Bromine DAMAO CHEMICAL REAGENT FACTORY 7726-95-6 Highly toxic
Triphenylene   HWRK Chem HWG45510
Iron powder Sigma-Aldrich 12310
Nitrobenzene DAMAO CHEMICAL REAGENT FACTORY 2934
Diethyl ether  DAMAO CHEMICAL REAGENT FACTORY 48
Dichloromethane DAMAO CHEMICAL REAGENT FACTORY 3067
Sodium metal J&K WM-NMS-54-25X-50G Air sensitive
Tetrahydrofuran J&K 315353
Dimethyl disulfide INTERNATIONAL LABORATORY USA 726415
1,3-Dimethyl-2-imadazolidinone J&K 50483 Dried over 4Å sieves
Valeryl  chloride J&K 99590
Methanol Guangzhou Chemical Reagent Factory 2334
Sodium hydroxide Guangzhou Chemical Reagent Factory 1588
Ethylene diamine Riedel-de Haën 15070
Lead acetate trihydrate PEKING CHEMICAL WORKE 861218
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Tags

Keywords: Thiol LinkerMetal-sulfur FrameworkCrystallizationSemiconducting GyroidalThioesterMercaptanMetal IonsSodium ThiomethoxideHVaTT Synthesis
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Citazione di questo articolo
He, Y., Huang, J., He, J., Xu, Z. Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework. J. Vis. Exp. (134), e57455, doi:10.3791/57455 (2018).
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