Name: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers (Video) | JoVE
Uploaded: 2023-05-12T14:20:00
Description: Watch this Scientific Journal Video about Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers at JoVE.com

这项工作得到了美国国家科学基金会化学部的资助，奖励号为CHE-2153240。

1. 设置舒伦克生产线
<ol><li>确保所有水龙头均已关闭，然后使用O形圈将冷阱固定到舒伦克生产线上（我们的设置中使用了229号，尽管尺寸可能因所使用的特定舒伦克生产线而异）并夹紧。</li>
	<li>打开真空泵（气镇关闭），然后打开舒伦克管线的水龙头，使整个设备打开真空。 注意：请勿打开软管的任何水龙头或任何其他对空气开放的水龙头;该设备应为动态真空下的封闭系统。<...

Synthesis of Low-Valent MOFs from Multitopic Phosphine Linkers

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A., Beller, M., Paciello, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Applied Homogeneous Catalysis with Organometallic Compounds: A Comprehensive Handbook in Four Volumes. , (2017).</li><li>Young, R. J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Isolating+reactive+metal-based+species+in+metal-organic+frameworks+-+Viable+strategies+and+opportunities.">Isolating reactive metal-based species in metal-organic frameworks - Viable strategies and opportunities.</a> Chemical Science. 11 (16), 40314050 (2020).</li><li>Drake, T., Ji, P., Lin, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Site+isolation+in+metal-organic+frameworks+enables+novel+transition+metal+catalysis.">Site isolation in metal-organic frameworks enables novel transition metal catalysis.</a> Accounts of Chemical Research. 51 (9), 21292138 (2018).</li><li>Dunning, S. G., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+metal-organic+framework+with+cooperative+phosphines+that+permit+post-synthetic+installation+of+open+metal+sites.">A metal-organic framework with cooperative phosphines that permit post-synthetic installation of open metal sites.</a> Angewandte Chemie - International Edition. 57 (30), 92959299 (2018).</li><li>Sikma, R. E., Balto, K. P., Figueroa, J. S., Cohen, S. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal-organic+frameworks+with+low-valent+metal+nodes.">Metal-organic frameworks with low-valent metal nodes.</a> Angewandte Chemie - International Edition. 61 (33), e202206353 (2022).</li><li>Agnew, D. W., Gembicky, M., Moore, C. E., Rheingold, A. L., Figueroa, J. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Robust,+transformable,+and+crystalline+single-node+organometallic+networks+constructed+from+ditopic+m-terphenyl+isocyanides.">Robust, transformable, and crystalline single-node organometallic networks constructed from ditopic m-terphenyl isocyanides.</a> Journal of the American Chemical Society. 138 (46), 1513815141 (2016).</li><li>Agnew, D. W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Crystalline+coordination+networks+of+zero-valent+metal+centers:+Formation+of+a+3-dimensional+Ni(0)+framework+with+m-Terphenyl+diisocyanides.">Crystalline coordination networks of zero-valent metal centers: Formation of a 3-dimensional Ni(0) framework with m-Terphenyl diisocyanides.</a> Journal of the American Chemical Society. 139 (48), 1725717260 (2017).</li><li>Voigt, L., Wugt Larsen, R., Kubus, M., Pedersen, K. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Zero-valent+metals+in+metal-organic+frameworks:+fac-M(CO)(3)(pyrazine)(3/2).">Zero-valent metals in metal-organic frameworks: fac-M(CO)(3)(pyrazine)(3/2).</a> Chemical Communications. 57 (3), 3861 (2021).</li><li>Sikma, R. E., Cohen, S. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal-organic+frameworks+with+zero+and+low-valent+metal+nodes+connected+by+tetratopic+phosphine+ligands.">Metal-organic frameworks with zero and low-valent metal nodes connected by tetratopic phosphine ligands.</a> Angewandte Chemie - International Edition. 61 (11), e202115454 (2022).</li><li>Xu, Z., Han, L. L., Zhuang, G. 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M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Capturing+chemical+intuition+in+synthesis+of+metal-organic+frameworks.">Capturing chemical intuition in synthesis of metal-organic frameworks.</a> Nature Communications. 10 (1), 17 (2019).</li></ol>

协议中必须遵循几个关键步骤，才能获得具有足够结晶度的所需膦基LVMOF产品。首先是金属前驱体和调节剂混合物（在这种情况下，分别为四（三苯基膦）钯（0）和三苯基膦）必须独立于多主题膦接头（在本例中为 Sn1）溶解。这是为了避免快速和不可逆地形成无定形配位聚合物，当调节剂相对于接头的有效浓度太低或根本不存在调节剂时，就会发生这种情况15。相?...

金属有机骨架（MOF）是一类结晶多孔材料1。MOF由金属离子或金属离子簇节点（通常称为二级建筑单元（SBU））和多主题有机接头构成，以提供二维和三维网络结构2。在过去的三十年中，由于MOFs在气体储存3 和分离4，生物医学5和催化6中的潜在用途，MOFs得到了广泛的研究。报道的绝大多数MOFs由高氧化态金属节点和坚硬的阴离子供体接头组成，例如羧酸盐2。然而，许多均相催化剂利用软的低价金属与软供体配体（如膦7）结合使用。因此，扩大含有低价金属的MOF的范围可以增加MOFs可以应用的催化转化范围。
使用嵌入软供体位点将低价金属掺入MOFs的既定策略范围有限，并且减少了母体MOF结构6，8，9，10的自由孔体积。另一种方法是直接使用低价金属作为节点或SBU，结合多主题软供体配体作为接头来构建MOF。该策略不仅在MOF中提供了低价金属位点的高负载量，而且由于框架结构的稳定性，还可以减少或防止金属浸入溶液中11。例如，Figueroa及其同事使用多位异腈配体作为软供体接头，使用Cu（I）12或Ni（0）13作为低价金属节点来产生二维和三维MOF。同样，Pederson及其同事使用吡嗪作为接头14合成了含有零价基团6金属节点的MOF。最近，我们的实验室报道了四位膦配体作为构建含有Pd（0）或Pt（0）节点的MOF的接头（图1）15。由于磷化氢连接低价金属配合物在均相催化中普遍存在，这些MOFs特别有趣7。然而，低价MOFs（LVMOFs）作为一类通用材料在MOF文献中的探索相对不足，但在叠氮化物-炔烃偶联16、铃木-宫浦偶联17，18、加氢17等反应的非均相催化中具有很大的应用前景11。
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/65317/65317fig01v2.jpg"> 图1：使用磷化氢接头合成LVMOF。 Sikma和Cohen15 报道了三维LVMOFs的合成， E1-M使用四位膦配体E1作为接头， Pd（0）和Pt（0）作为节点，三苯基膦作为调节剂。中心原子 E可以是Si或Sn. <a href="https://www.jove.com/files/ftp_upload/65317/65317fig01largev2.jpg" target="_blank">请点击这里查看此图的大图。</a>
虽然与传统MOF材料相比，LVMOF接头和节点的性质差异可能赋予它们独特的性能，但这些差异也带来了合成挑战。例如，MOF文献中常用的许多金属前驱体和接头可用于空气2。相比之下，成功合成基于磷化氢的LVMOF需要排除空气和水15。同样，与大多数MOF文献中使用的调节剂类型相比，用于促进结晶度的调节剂类型和用于合成膦基LVMOF的溶剂是不寻常的15。因此，这些材料的合成需要设备和实验技术，即使是经验丰富的MOF化学家也可能不太熟悉。因此，为了尽量减少这些障碍的影响，这里提供了一种合成这种新型材料的分步方法。这里概述的方案涵盖了合成磷化氢基LVMOF的所有方面，包括整体实验程序，无空气技术，所需设备，LVMOF的正确储存和处理以及表征方法。还讨论了金属前驱体、调节剂和溶剂的选择。使新研究人员能够进入该领域将有助于加速发现用于催化应用的新型LVMOF和相关材料。

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>2800 Ultrasonic Cleaner, 3/4 Gallon, 40 kHz</td>
			<td>Branson</td>
			<td>CPX2800H</td>
			<td>Used for sonicating</td>
		</tr>
		<tr>
			<td>Argon, Ultra High Purity</td>
			<td>Matheson</td>
			<td>G1901101</td>
			<td>Used as inert gas source</td>
		</tr>
		<tr>
			<td>D8 ADVANCE Powder X-Ray Diffractometer</td>
			<td>Bruker</td>
			<td></td>
			<td>Used to collect PXRD patterns</td>
		</tr>
		<tr>
			<td>Dewar Flask</td>
			<td>Chemglass Life Sciences</td>
			<td>CG159303</td>
			<td>Dewar used for liquid nitrogen</td>
		</tr>
		<tr>
			<td>Flask,&#160;High Vacuum Valve, Capacity (mL) 10, Valve Size 0-4 mm</td>
			<td>Synthware Glass</td>
			<td>F490010</td>
			<td>Reaction vessel referred to as &#34;10 mL flask&#34;</td>
		</tr>
		<tr>
			<td>Grade 2 Qualitative Filter Paper, Standard, 42.5 mm circle</td>
			<td>Whatman</td>
			<td>1002-042</td>
			<td>Used for product isolation</td>
		</tr>
		<tr>
			<td>Methylene Chloride (HPLC)</td>
			<td>Fisher Scientific</td>
			<td>MFCD00000881</td>
			<td>Dried and deoxygenated prior to use</td>
		</tr>
		<tr>
			<td>Sn1 (tetratopic phosphine linker)</td>
			<td></td>
			<td></td>
			<td>Prepared according to literature procedure (ref. 15)</td>
		</tr>
		<tr>
			<td>SuperNuova+ Stirring Hotplate</td>
			<td>Thermo Fisher Scientific</td>
			<td>SP88850190</td>
			<td>Used to heat oil bath</td>
		</tr>
		<tr>
			<td>Tetrakis(triphenylphosphine) palladium(0), 99% (99.9+%-Pd)</td>
			<td>Strem Chemicals</td>
			<td>46-2150</td>
			<td>Commercial Pd(0) source</td>
		</tr>
		<tr>
			<td>Toluene (HPLC)</td>
			<td>Fisher Scientific</td>
			<td>MFCD00008512</td>
			<td>Dried and deoxygenated prior to use</td>
		</tr>
		<tr>
			<td>Triphenylphosphine, &#8805;95.0% (GC)</td>
			<td>Sigma-Aldrich</td>
			<td>93092</td>
			<td>Used as a modulator</td>
		</tr>
		<tr>
			<td>Weighing Paper</td>
			<td>Fisher Scientific</td>
			<td>09-898-12B</td>
			<td>Used for solid addition</td>
		</tr>
	</tbody>
</table>

experimental approaches for the synthesis of low-valent metal-organic frameworks from multitopic phosphine linkers

金属有机骨架（MOF）因其在气体储存和分离、生物医学、能源和催化方面的潜在应用而成为人们关注的焦点。最近，人们探索了低价MOFs（LVMOFs）作为非均相催化剂的潜在用途，多位磷化氢接头已被证明是形成LVMOF的有用构建块。然而，使用磷化氢接头合成LVMOF需要与大多数MOF合成文献不同的条件，包括排除空气和水以及使用非常规调节剂和溶剂，这使得获取这些材料更具挑战性。这项工作是用磷化氢接头合成LVMOF的一般教程，包括以下内容的信息：1）金属前驱体、调节剂和溶剂的明智选择;2）实验程序、无气技术和所需设备;3）正确储存和处理由此产生的LVMOF;4）这些材料的有用表征方法。本报告的目的是降低MOF研究这一新子领域的门槛，并促进新型催化材料的进步。

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

成功合成Sn1-Pd产生亮黄色结晶固体。使用类似四位膦接头的Pd（0）MOF产物也是黄色的。确定反应是否成功的最有效方法是收集PXRD图谱并评估样品的结晶度。例如，图2显示了晶体Sn1-Pd的PXRD图谱。验证样品是否结晶的关键特征是反射峰相对尖锐且基线平坦。峰展宽通常表示无定形材料。为了说明这一点，图3显示了Sn1-Pd</stro...

Watch this Scientific Journal Video about Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers at JoVE.com

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers (Video) | JoVE 

在这里，我们描述了在无空气条件下从低价金属和多主题磷化氢接头合成低价金属有机框架（LVMOF）的方案。所得材料作为模拟低价金属基均相催化剂的多相催化剂具有潜在的应用前景。

多位膦接头合成低价金属有机骨架的实验方法

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, ...

我们的研究旨在探索由低价金属离子构建的金属有机骨架的合成和性质。如何制备这些材料及其特性尚未得到广泛了解，但它们可能为固态催化和其他应用提供了巨大的机会。除了我们自己的工作之外，只有少数关于由低价金属离子制备的MOF的报告。也许最值得注意的是加州大学圣地亚哥分校的Joshua Figueroa教授的那些，他描述了由笨重的异氰酸酯配体和零价或一价金属制备的MOF。由于对低价MOF的描述很少，我们的协议提供了用于制造这些材料的第一个基线协议。也就是说，我们的方案是专门为磷化氢配体设计的，可能不容易转化为不同的配体系统，如异氰酸酯。我们的发现为探索具有与迄今为止描述的大多数MOF不同特征的MOF材料提供了机会。例如，我们有一篇新论文报道了Vaska复合物的固态类似物，与其他少数这样做的MOF相比，它以独特的方式可逆地结合氧气。我们有兴趣为制造低价MOFs开辟新的机会，特别是作为新的固态催化剂。我们想回答这样的问题：还有哪些低价金属离子可以用来制造LV MOF，我们是否可以使用这些固态材料模拟低价化合物的反应性？