Name: synthesis of a water-soluble metal–organic complex array
Uploaded: 2016-10-08T14:00:00.000+00:00
Duration: 6 min 40 s
Description: Watch this Scientific Journal Video about Synthesis of a Water-soluble Metalâ€“Organic Complex Array at JoVE.com

This work was supported by the World Premier International Research Center (WPI) Initiative on Materials Nanoarchitectonics and a Grant-in-Aid for Challenging Exploratory Research (No. 26620139), both of which were provided from MEXT, Japan.

1.金属络合物的单体制备（2 CAS RN 1381776-70-0，3 CAS RN 1261168-42-6，4 CAS RN 1261168-43-7;图1） <ol><li> 茹单体2的制备 <ol><li>在一个有搅拌棒（380毫克，0.48毫摩尔）和[Ru（ 对 -cymene）Cl 2中]二聚体（224毫克，0.37毫摩尔）;合并有机前体（ 图1 5 9 CAS RN 1381776-63-1）百毫升单颈圆底烧瓶中。 </li><li>添加甲醇（MeOH）（25ml）中的混合物，冷凝器连接到烧瓶的接头，并搅拌在65℃的悬浮液用于在温度控制的油浴中3小时。 </li><li>冷却反应混合物至室温，并通过抽吸通过滤纸过滤悬浮液。 </li><li>洗在过滤器上用MeOH彻底残余物直至滤液变为肉眼无色干燥，减压残余物中。 </li><li>结合将残余物和4&#39; - （4-甲基苯基）-2,2&#39;:6＆＃39，2" - 三联吡啶（216毫克，0.68毫摩尔）在100毫升单颈圆底烧瓶中搅拌棒。 </li><li>添加甲醇（22.5毫升）和水（2.5毫升）到混合物中，冷凝器连接到烧瓶的接头，并搅拌在70℃的悬浮液16小时。 </li><li>冷却反应混合物至室温，并过滤悬浮液。 </li><li>干上在减压下过滤残余物，并在二甲亚砜（DMSO）（3毫升）溶解。 </li><li>缓慢加入DMSO溶液至过量的乙酸乙酯（EtOAc）。 </li><li>过滤所得悬浮液，洗上用EtOAc过滤残余物，并减压干燥。 </li></ol></li><li> 铂单体3的制备 <ol><li>在搅拌棒（360毫克，0.50毫摩尔）和Pt（环辛-1,5-二烯）Cl 2中（195毫克，0.52毫摩尔）;合并有机前体（ 图1 6 4 CAS RN 1261168-39-1）的100毫升单颈圆底烧瓶中。&lt;/ LI&gt; <li>添加甲醇（15毫升）到混合物中，冷凝器连接到烧瓶的接头，并搅拌在65℃的悬浮液12小时。 </li><li>冷却反应混合物至室温，并过滤悬浮液。 </li><li>洗在过滤器上用MeOH彻底残余物并在减压下干燥。 </li></ol></li><li> 铑单体4的制备 <ol><li>有搅拌棒（360毫克，0.50毫摩尔）和RhCl 3·3H 2 O（137毫克，0.52毫摩尔）在100毫升单颈圆底烧瓶中;合并有机前体（ 图1 6）。 </li><li>添加甲醇（50毫升）到混合物中，冷凝器连接到烧瓶的接头，并在N 2气氛下搅拌在65℃下12小时的悬浮液。 </li><li>冷却反应混合物至室温，并过滤悬浮液。 </li><li>洗在过滤器上用MeOH彻底残余物并在减压下干燥。 </li></ol></li></o升&gt; 2.制备水溶性金属 - 有机络合物阵列1 <ol><li> Fmoc去保护从TG锡伯树脂 <ol><li>在10毫升2-颈烧瓶轴承在装有玻璃过滤器的底部的漏极和一个2路止水栓（ 图2a）有搅拌棒结合作为购买的TG塞伯树脂（135毫克）。连接一个3路活栓和玻璃塞的烧瓶的接头。 </li><li>通过使用真空管线交换用N 2的内部气氛，然后溶胀用无水级二氯甲烷（CH 2 Cl 2中）（1毫升）（ 图2b）的树脂。 </li><li>在这个顺序加无水级二甲基甲酰胺（DMF）（3ml）和哌啶（1ml）中并搅拌，在室温下2.5小时的混合物。 </li><li>除去通过过滤通过排水的溶液。洗，用无水级甲醇树脂（3毫升，3分钟搅拌）和无水级的 CH 2 Cl 2（3毫升，3分搅拌）交替三次，然后用无水级的 CH 2 Cl 2（3毫升，3分钟搅拌）的四倍（ 图2c）。 </li><li>结合在2.1.4中获得的所有解决方案，并用乙腈（CH 3 CN）的50毫升体积稀释它们。转移得到的溶液的等分试样（1ml）中成石英杯中以1厘米的光学长度，用CH 3 CN（2毫升）稀释。 </li><li>确定（a）到协议中制备的溶液中，根据以下2.1.5的摩尔数基于（在299纳米6,234）哌啶二苯并富烯的加合物的消光系数脱保护的Fmoc基团（ 六微摩尔）10和光谱得到的吸光度方程: F = 0.05×10 6×3× 一个 / 6234 </li></ol></li><li> 茹单体2装载 <ol><li>加无水级的 CH 2 Cl 2（2.5毫升），钌单体2 </s仲&gt;（64.9毫克，53.2微摩尔），2-（1H-苯并三唑-1-基）-1,1,3,3-四甲基脲六氟磷酸盐（HBTU）（30.3毫克，79.8微摩尔），无水级的DMSO（2.5毫升），和N，N-二异丙基乙胺（ⅰPR 2 NET）（20微升）的顺序在N 2气氛中经洗涤的树脂下，搅拌在室温下（ 图2d）12小时的混合物。 </li><li>除去通过过滤通过排水的溶液。用无水级的DMSO洗涤树脂（3毫升，搅拌5分钟）三次，无水级的MeOH（3毫升，3分钟搅拌）和无水级的 CH 2 Cl 2（3毫升，3分钟搅拌）交替三次和无水级的 CH 2 Cl 2（3毫升，3分钟搅拌）三次。 </li><li>在该顺序的 N 2气氛下，添加无水同类的 CH 2 Cl 2（5毫升），苯甲酸酐（0.28克，1.5毫摩尔）和N-甲基咪唑（0.10毫升，1.5毫摩尔）加入到洗涤树脂并搅拌该混合物在室温下2小时。 </li><li>除去通过过滤通过排水的溶液。洗，用无水级的 CH 2 Cl 2中的树脂（3毫升，3分钟搅拌）和无水级的MeOH（3毫升，3分钟搅拌）交替三次，然后用无水级的 CH 2 Cl 2（3毫升，3分搅拌）三次。 </li><li>重复该协议在2.1.3-2.1.6所述量化摩尔数加载茹单体2。 </li></ol></li><li> 的Fmoc-和侧残余叔丁基（ 叔丁基）的装载-protected（L）l-谷氨酸（谷氨酸）（7 CAS RN 71989-18-9;图1） <ol><li>添加无水级二氯甲烷 （4.5毫升），谷氨酸·H 2 O（39.4毫克，88.8微摩尔），HBTU（50.5毫克，133.2微摩尔），无水级DMSO（0.5毫升），和我 PR 2 NET（ 50微升）在N 2气氛中加入到洗涤树脂根据这个命令并搅拌该混合物，在室温德12小时温度（ 图2e）。 注:谷氨酸的量·H 2 O和HBTU逐渐从步骤2.3至2.7，以保持它们的化学计量在树脂恒定反应性-NH 2功能的降低。 </li><li>重复该协议在2.2.2-2.2.4描述。 </li><li>取树脂的一小部分出烧瓶，放入三氟乙酸（CF 3 CO 2 H）（2.5微升），三乙基硅烷（的Et 3 SiH基）（0.5微升）的混合物，和1,2-二氯乙烷（ 47微升）。超声处理的混合物0.5小时，并使用为质谱-4,7,8,9-（ 图3a）所得到的溶液中。 </li><li>重复该协议在2.1.3-2.1.6所述量化摩尔数加载谷氨酸。 </li></ol></li><li> 铂单体3装载 <ol><li>添加无水级的DMSO（4.5毫升），铂单体（32.9毫克，33.3微摩尔），HBTU（18.9毫克，50.0微摩尔），无水级CH 2Cl 2中（0.5毫升）， 我镨2净（20微升）在N 2气氛中经洗涤的树脂根据这个命令，搅拌在室温下（ 图2f）的 12小时的混合物。 </li><li>重复该协议在2.2.2-2.2.5所述量化摩尔数加载铂单体3。 </li></ol></li><li> 谷氨酸装载 <ol><li>添加无水级二氯甲烷 （4.5毫升），谷氨酸·H 2 O（27.8毫克，62.9微摩尔），HBTU（35.8毫克，94.4微摩尔），无水级DMSO（0.5毫升），和我 PR 2 NET（ 50微升）在N 2气氛中经洗涤的树脂根据这个命令，搅拌在室温下12小时的混合物。 </li><li>重复该协议中2.3.2-2.3.4（ 图3b）所描述。 </li></ol></li><li> 铑单体4加载 <ol><li>添加无水级的DMSO（4.5毫升）中，铑单体4（21.8毫克，23.3微摩尔），HBTU（13.3毫克，35.0微摩尔），无水级二氯甲烷 （0.5毫升），和我镨2 NET（20微升）在N 2气氛到洗涤树脂根据这个命令，搅拌混合物在室温下（ 图2G）12小时。 </li><li>重复该协议在2.2.2中描述。 </li><li>重复该协议在2.6.1中描述。 </li><li>重复该协议在2.2.2-2.2.5所述量化摩尔数加载的Rh单体4。 </li></ol></li><li> 谷氨酸装载 <ol><li>添加无水级二氯甲烷 （4.5毫升），谷氨酸·H 2 O（20.4毫克，46.0微摩尔），HBTU（26.2毫克，69.0微摩尔），无水级DMSO（0.5毫升），和我 PR 2 NET（ 50微升）在N 2气氛中经洗涤的树脂根据这个命令，搅拌在室温下12小时的混合物。 </li><li>重复该协议在2.3.2-2.3.4描述（图3c）。 </li></ol></li><li> 2-装载[2-（2-甲氧基乙氧基）乙氧基]乙酸（TEG）酸（8 CAS RN 16024-58-1;图1） <ol><li>加无水级的 CH 2 Cl 2（3毫升），三甘醇酸（14微升，91.0微摩尔），HBTU（51.7毫克，136.5微摩尔），无水级的 CH 2 Cl 2（2ml）中， 我 PR 2净（ 50微升）在N 2气氛中经洗涤的树脂根据这个命令，搅拌在室温下12小时的混合物。 </li><li>除去通过过滤通过排水的溶液。用无水级的DMSO洗涤树脂（3毫升，搅拌5分钟）两次，无水级的MeOH（3毫升，3分钟搅拌）和无水级的 CH 2 Cl 2（3毫升，3分钟搅拌）交替三次和无水级的 CH 2 Cl 2（3毫升，3分钟搅拌）三次。 </li></ol></li><li> 从树脂裂解在固相合成结束时 <ol><li>洗用乙醚（4毫升，搅拌5分钟）三次，所述树脂干它的真空下，用无水级的 CH 2 Cl 2溶胀它（1毫升，搅拌5分钟）。 </li><li>添加CF 3 CO 2 H（0.1毫升），乙醚3的SiH（20微升），和1,2-二氯乙烷（1.9毫升）中的悬浮液的混合物中，搅拌，在室温下12小时的混合物。 </li><li>通过漏极除去通过过滤该溶液，加入CF的新的混合物3 CO 2 H（0.1毫升），乙醚3的SiH（20微升），和1,2-二氯乙烷（1.9毫升）中的树脂，并搅拌该混合物在室温下1小时。 </li><li>重复步骤2.9.3至溶液变为肉眼无色（ 图2h）。 </li><li>结合所有的解决方案，通过协议2.9.2-2.9.4获得并通过质谱法-4,7,8,9-（ 图3d）分析所得溶液中的内容。 </li><li>除去由evaporatio溶液的挥发性物质n和溶解残余物中的CF 3 CO 2 H（0.2mL）中，的Et 3 SiH基（40微升），和1,2-二氯乙烷（3.8毫升）的混合物中。 </li><li>搅拌在室温下24小时的混合物中，并通过质谱法-4,7,8,9-分析所得溶液的内容物在1（ 图3e）的侧面的残基，以证实T卜组的完全脱保护。 </li><li>除去通过蒸发该溶液的挥发性物质。 </li></ol></li><li> 1纯化 <ol><li>超声处理固体残渣通过协议2.9在CH 2 Cl 2得到，倒出溶液。直到澄清溶液变成无色视觉重复此过程。 </li><li>通过质谱法-4,7,8,9-分析所得固体残余物中的内容。 </li><li>用MeOH（100微升/ 10毫克）与超声处理洗涤残余物，滗析该溶液，并分析所得到的S中的内容通过质谱法-4,7,8,9-奥利德残基。 </li><li>溶解在通过超声处理一个CH 3 CN（90微升）和水（10微升）的混合物中的残余物（1毫克）中，用磷酸盐缓冲盐水（800微升，10毫米，pH值= 7.4）得到的溶液相结合。超声处理混合物，并在37℃下孵育其24小时。 </li><li>提取在澄清上清液中的有色物质与1,2-二氯乙烷（500微升），CH 3 CN（20微升），和CF 3 CO 2 H（20微升）的混合物中。分析通过质谱法-4,7,8,9-（ 图3f）的提取物。 </li><li>重复萃取直到水相变为肉眼无色。合并有机溶液，并通过蒸发除去挥发性物质。 </li></ol></li></ol>

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The authors have nothing to disclose.

完美除去从树脂上不希望的化学物质的不总是可能简单地通过与可以容易地溶解的化学品的溶剂洗涤。一个关键的技术能够有效地洗涤树脂是以使其膨胀并反复收缩，使剩余的内部的化学品将被压出。这就是为什么在我们的程序将树脂用CH 2 Cl 2和MeOH处理交替，因为它是洗涤（ 例如，协议2.1.4）。 作为连续多非量化偶联反应的结果，在作为切割的混合物针对性阵列的固相合成结束时的量可以是小的。尽管在固相合成每个反应通常只进行一次，在同一偶联反应可以重复多次，如在协议2.6例举，如果有必要提高相应的反应步骤的总耦合产率。通过重复相同coupli纳克反应两次，可以实现大的〜10％的相应偶联反应的产率。 相反通常用于固相多肽合成的Fmoc保护的氨基酸的单体，那些对多金属肽阵列的金属络合物单体一般显示在他们的偶合反应在树脂的表面上的不超过80％的产率。空间效应由于体积大的金属络合物部分的存在发挥作用，因为一个氨基酸单元的单体的C末端的插入有时大幅度改善其耦合产量。然而，即使是这样的单体结构的修改都仍然是不够的，以优化量化偶联反应。这是要在未来，特别是对于通过这种方法的全过程的自动化的高通量生产多金属肽阵列解决的问题，如已经建立的在固相多肽合成的情况下。 </p&gt; 与溶液相合成相比，固相合成的一个重要优点是附加到从其它化学品通过过滤和洗涤溶液中的树脂，与能够溶解它们的溶剂的产品容易分离11这是特别有用多金属物种，其分离的合成/提纯不易与其他方法。因此，协议强调这里是唯一现实的选择，以使具有三个或更多个不同的金属的一个预定序列多金属肽阵列。此外，由于这种方法的简单性，该协议可以覆盖生产宽得多的范围多金属异核络合物比从已经存在的合成方法1,2,3访问的。 如用这种方法产生的化合物具有的沿着肽骨架金属中心完全控制的序列，它们是上诉ING候选调查这种序列调节结构上与生物相关的分子的相互作用（ 例如，肽，蛋白质，核酸，和糖，这也有在其结构中经调节序列）的影响。这是我们的激励，使产品是水溶性的。

复杂分子结构的控制合成一直是合成化学的一个重大问题。从这个观点来看，以合成多核异金属配合物在一个可设计方式仍然是一个值得受试者中，因为通常用于从基配体的金属化的方法可能的结构的结果的数字无机化学领域中受到挑战编制单体金属配合物。虽然多核异金属配合物的几个例子迄今1,2,3报道，试验和错误或它们的合成的艰巨性就必须一个简单的方法，该方法适用于大范围的结构的的发展。 作为一种新的方法来解决这个问题，在2011年，我们报道了合成方法4,5在具有Fmoc保护氨基酸部分单核的各种金属络合物依次偶合，得到多通过固相多肽合成6的协议金属肽阵列。由于多肽合成的连续性质，多个金属中心的特定序列是通过控制那些金属络合物单体的偶联反应的数量和顺序合理设计性。以后，该方法进一步模块化通过用两个较短的阵列7之间的共价键相结合，使各种更大和/或支链的阵列结构。 在这里，我们将展示如何这样多金属肽阵列的合成通常是通过选择最近报道WSMOCA（1 8 CAS RN 1827663-18-2; 图1）操作作为代表例。虽然一个特定阵列的合成在此协议的描述，相同的程序适用于宽范围的不同的序列，各异构体9的合成。我们预计，这一原山口将激发更多的研究人员参加序列控制化合物的科学，其中该分子研究迄今还典型地是生物聚合物，但很少包括的金属配合物为基础的物种的例子。

<table><tbody><tr><td>Dichloro(1,5-cyclooctadiene)platinum(II)</td><td>TCI</td><td>D3592</td><td></td></tr><tr><td>Rhodium(III) chloride trihydrate</td><td>Kanto Chemical</td><td>36018-62</td><td></td></tr><tr><td>Phosphate buffered saline, tablet</td><td>Sigma Aldrich</td><td>P4417-50TAB&amp;nbsp;</td><td></td></tr><tr><td>NovaSyn TG Sieber resin</td><td>Novabiochem</td><td>8.55013.0005</td><td></td></tr><tr><td>HBTU</td><td>TCI</td><td>B1657</td><td></td></tr><tr><td>Benzoic anhydride</td><td>Kanto Chemical</td><td>04116-30</td><td></td></tr><tr><td>Trifluoroacetic acid</td><td>Kanto Chemical</td><td>40578-30</td><td></td></tr><tr><td>Triethylsilane</td><td>TCI</td><td>T0662</td><td></td></tr><tr><td>2-[2-(2-Methoxyethoxy)ethoxy]acetic acid</td><td>Sigma Aldrich</td><td>407003</td><td>Dried over 3 &amp;Aring; sieves</td></tr><tr><td>Dithranol</td><td>Wako Pure Chemical Industries</td><td>191502</td><td></td></tr><tr><td>&lt;em&gt;N&lt;/em&gt;-methylimidazole</td><td>TCI</td><td>M0508</td><td></td></tr><tr><td>Piperidine</td><td>Kanto Chemical</td><td>32249-30</td><td></td></tr><tr><td>4&#039;-(4-methylphenyl)-2,2&#039;:6&#039;,2&quot;-terpyridine</td><td>Sigma Aldrich</td><td>496375</td><td></td></tr><tr><td>Dehydrated grade dimethylsulfoxide</td><td>Kanto Chemical</td><td>10380-05&amp;nbsp;</td><td></td></tr><tr><td>Dehydrated grade methanol</td><td>Kanto Chemical</td><td>25506-05&amp;nbsp;</td><td></td></tr><tr><td>Dehydrated grade dichloromethane</td><td>Kanto Chemical</td><td>11338-84</td><td></td></tr><tr><td>MeOH</td><td>Kanto Chemical</td><td>25183-81&amp;nbsp;</td><td></td></tr><tr><td>Dimethylsulfoxide</td><td>Kanto Chemical</td><td>10378-70</td><td></td></tr><tr><td>Ethyl acetate</td><td>Kanto Chemical</td><td>14029-81</td><td></td></tr><tr><td>Acetonitrile</td><td>Kanto Chemical</td><td>01031-70&amp;nbsp;</td><td></td></tr><tr><td>1,2-dichloroethane</td><td>Kanto Chemical</td><td>10149-00</td><td></td></tr><tr><td>Diethyl ether</td><td>Kanto Chemical</td><td>14134-00&amp;nbsp;</td><td></td></tr><tr><td>Dichloromethane</td><td>Kanto Chemical</td><td>10158-81</td><td></td></tr></tbody></table>

synthesis of a water-soluble metal&#8211;organic complex array

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as Ru(II), Pt(II), and Rh(III). The compound, named as a water-soluble metal-organic complex array (WSMOCA), is obtained through 1) the conventional solution-chemistry-based preparation of the corresponding metal complex monomers having a 9-fluorenylmethyloxycarbonyl (Fmoc)-protected amino acid moiety and 2) their sequential coupling together with other water-soluble organic building units on the surface-functionalized polymeric resin by following the procedures originally developed for the solid-phase synthesis of polypeptides, with proper modifications. Traces of reactions determined by mass spectrometric analysis at the representative coupling steps in stage 2 confirm the selective construction of a predetermined sequence of metal centers along with the peptide backbone. The WSMOCA cleaved from the resin at the end of stage 2 has a certain level of solubility in aqueous media dependent on the pH value and/or salt content, which is useful for the purification of the compound.

图1示出的最终目标化合物，前体，和中间体的分子结构， 图2示出了树脂的图像和图3示出的样品中的选定的过程的步骤的MALDI-TOF质谱。从图2a的图像至2h显示的，因为它在该协议的第2反应步骤经历的树脂的颜色和外观的变化。 MALDI-TOF质谱法用于跟踪反应，并确认目标物质的存在预期。 <img alt="图1" src="/files/ftp_upload/54513/54513fig1.jpg" /> 图 1. WSMOCA，前体和中间体的分子结构 （1）的目标WSMOCA。 （2，3，4）的钌，铂，和Rh单体，分别; （5），用于钌单体2的有机前体; （6）为铂单体3和Rh单体4的有机前体; （7）谷氨酸; （8）三甘醇酸;在2.3.3，2.5.2进行检测（9，10，11）合成中间体和2.7.2分别。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/54513/54513fig1large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图2" src="/files/ftp_upload/54513/54513fig2.jpg" /> 图2 的树脂的外观在选定的合成步骤的照片（a）在购买的TG塞伯树脂在2.1.1的玻璃器皿为固相合成。 （b）该树脂在CH 2溶胀Cl 2中</sUB&gt;在2.1.2; （C）的Fmoc集团在2.1.4脱保护后洗涤树脂; （ 四 ）悬浮于钌单体2中的2.2.1加载溶液的树脂; （ 五 ）悬浮于谷氨酸在2.3.1加载溶液的树脂; （ 六 ）悬浮在铂单体3在2.4.1加载一个解决方案的树脂; （G）悬浮在用于Rh单体4在2.6.1加载溶液的树脂; （H）悬浮在裂解反应的解决方案在2.9.4树脂。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/54513/54513fig2large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图3" src="/files/ftp_upload/54513/54513fig3.jpg" /> 图3. 1 determ的 编制痕迹通过质谱分析INED MALDI-TOF样品的质谱从树脂在固相合成的选定步骤裂解（过程（ 一 ）2.3.3确认9的存在;（B）2.5.2确认的10的存在;（ 三 ）2.7.2确认的11的存在;（D）2.9.5确认的1存在下）和那些样品在下面的步骤（步骤（E）2.9.7确认在1侧残留牛逼卜组的完全脱保护;（ 六 ）2.10.5，确认没有比1以外的任何重大信号）的<a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/54513/54513fig3large.jpg" target="_blank">请点击此处查看该图的放大版本。</a>

Watch this Scientific Journal Video about Synthesis of a Water-soluble Metalâ€“Organic Complex Array at JoVE.com

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

一个水溶性金属 - 有机络合物阵列合成

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

synthesis-of-a-water-soluble-metalorganic-complex-array

Nanyang Technological University

Research

JoVE Journal

Chemistry

9.8K 次观看.  National Institute for Materials Science. A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

视频: Synthesis of a Water-soluble Metal–Organic Complex Array

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

功能化的合成与表征金属 - 有机骨架

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

科研

化学

The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique

The number of well-characterized metalloid tin clusters, synthesized by applying the disproportionation of a metastable Sn(I) halide in the presence of a sterically demanding ligand, has increased in recent years. The metastable Sn(I) halide is synthesized at&#160;&#34;outer space conditions&#34; via the preparative co-condensation technique. Thereby, the subhalide is synthesized in an oven at high temperatures, around 1,300 &#176;C, and at reduced pressure by the reaction of elemental tin with hydrogen halide gas (e.g., HCl). The subhalide (e.g., SnCl) is trapped within a matrix of an inert solvent, like toluene at -196 &#176;C. Heating the solid matrix to -78 &#176;C gives a metastable solution of the subhalide. The metastable subhalide solution is highly reactive but can be stored at -78 &#176;C for several weeks. On heating the solution to room temperature, a disproportionation reaction occurs, leading to elemental tin and the corresponding dihalide. By applying bulky ligands like Si(SiMe3)3, the intermediate metalloid cluster compounds can be trapped before complete disproportionation to elemental tin. Hence, the reaction of a metastable Sn(I)Cl solution with Li-Si(SiMe3)3 gives [Sn10(Si(SiMe3)3)4]2- 1 as black crystals in high yield. 1 is formed via a complex reaction sequence including salt metathesis, disproportionation, and degradation of larger clusters. Further, 1 can be analyzed by various methods like NMR or single crystal X-ray structure analysis.

The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique

The disproportionation reaction of a metastable Sn(I) chloride solution, obtained via the preparative co-condensation technique, is used for the synthesis of a metalloid tin cluster compound.

的合成[锡<sub&gt; 10</sub&gt;（SI（SIME<sub&gt; 3</sub&gt;）<sub&gt; 3</sub&gt;）<sub&gt; 4</sub&gt;]<sup&gt; 2</sup<sup&gt; -</sup&gt;使用亚稳锡（I）卤溶液通过共缩聚合成技术

The number of well-characterized metalloid tin clusters, synthesized by applying the disproportionation of a metastable Sn(I) halide in the presence of a ...

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

半导体回转金属硫框架结晶的硫醇构建块的合成

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. However, the main issue limiting their applicability is their poor stability in humid conditions. The common methods to overcome this problem involve the formation of strong metal-linker bonds by using highly charged metals, which is limited to a number of structures, the introduction of alkylic groups to the framework by post-synthetic modification (PSM) or chemical vapour deposition (CVD) to enhance overall hydrophobicity of the framework. These last two usually provoke a drastic reduction of the porosity of the material. These strategies do not permit to exploit the properties of the MOF already available and it is imperative to find new methods to enhance the stability of MOFs in water while keeping their properties intact. Herein, we report a novel method to enhance the water stability of MOF crystals featuring Cu2(O2C)4&#160;paddle-wheel units, such as HKUST (where HKUST stands for Hong Kong University of Science &#38; Technology), with the catechols functionalized with alkyl and fluoro-alkyl chains. By taking advantage of the unsaturated metal sites and the catalytic catecholase-like activity of CuII ions, we are able to create robust hydrophobic coatings through the oxidation and subsequent polymerization of the catechol units on the surface of the crystals under anaerobic and water-free conditions without disrupting the underlying structure of the framework. This approach not only affords the material with improved water stability but also provides control over the function of the protective coating, which enables the development of functional coatings for the adsorption and separations of volatile organic compounds. We are confident that this approach could also be extended to other unstable MOFs featuring open metal sites.

Robust functional catechol coatings were produced in one step by direct reaction of the material known as HKUST with synthetic catechols under anaerobic conditions. The formation of homogeneous coatings surrounding the entire crystal is ascribed to the biomimetic catalytic activity of Cu(II) dimers on the external surface of the crystals.

金属-有机框架的表面功能化改善防潮性能

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. ...

Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks

Because of their designability and unprecedented synergistic effects, core-shell metal-organic frameworks (MOFs) have been actively examined recently. However, the synthesis of single-crystalline core-shell MOFs is very challenging, and thus a limited number of examples have been reported. Here, we suggest a method of synthesizing single-crystalline HKUST-1@MOF-5 core-shells, which is HKUST-1 at the center of MOF-5. Through the computational algorithm, this pair of MOFs was predicted to have the matched lattice parameters and chemical connection points at the interface. To construct the core-shell structure, we prepared the octahedral- and cubic-shaped HKUST-1 crystals as a core MOF, in which the (111) and (001) facets were mainly exposed, respectively. Via the sequential reaction, the MOF-5 shell was well-grown on the exposed surface, showing a seamless connect interface, which resulted in the successful synthesis of single-crystalline HKUST-1@MOF-5. Their pure phase formation was proved by optical microscopic images and powder X-ray diffraction (PXRD) patterns. This method presents the potential of and insights into the single-crystalline core-shell synthesis with different kinds of MOFs.

Here, we demonstrate a protocol for the two-step synthesis of single-crystalline core-shells using a non-isostructural metal-organic framework (MOF) pair, HKUST-1 and MOF-5, which have well-matched crystal lattices.

单晶核壳金属有机骨架的合成

Because of their designability and unprecedented synergistic effects, core-shell metal-organic frameworks (MOFs) have been actively examined recently. ...

从多主题膦接头合成低价 MOF

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

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, energy, and catalysis. Recently, low-valent MOFs (LVMOFs) have been explored for their potential use as heterogeneous catalysts, and multitopic phosphine linkers have been shown to be a useful building block for the formation of LVMOFs. However, the synthesis of LVMOFs using phosphine linkers requires conditions that are distinct from those in the majority of the MOF synthetic literature, including the exclusion of air and water and the use of unconventional modulators and solvents, making it somewhat more challenging to access these materials. This work serves as a general tutorial for the synthesis of LVMOFs with phosphine linkers, including information on the following: 1) the judicious choice of the metal precursor, modulator, and solvent; 2) the experimental procedures, air-free techniques, and required equipment; 3) the proper storage and handling of the resultant LVMOFs; and 4) useful characterization methods for these materials. The intention of this report is to lower the barrier to this new subfield of MOF research and facilitate advancements toward novel catalytic materials.

作者聚焦:从多主题膦接头合成低价金属有机框架的实验方法  

Here, we describe a protocol for the synthesis of low-valent metal-organic frameworks (LVMOFs) from low-valent metals and multitopic phosphine linkers under air-free conditions. The resulting materials have potential applications as heterogeneous catalyst mimics of low-valent metal-based homogeneous catalysts.

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, ...

三唑和四唑官能化 Zr-MOF 的合成和表征

Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange

Metal-organic frameworks (MOFs) are a class of porous materials that are formed through coordination bonds between metal clusters and organic ligands. Given their coordinative nature, the organic ligands and strut framework can be readily removed from the MOF and/or exchanged with other coordinative molecules. By introducing target ligands to MOF-containing solutions, functionalized MOFs can be obtained with new chemical tags via a process called post-synthetic ligand exchange (PSE). PSE is a straightforward and practical approach that enables the preparation of a wide range of MOFs with new chemical tags via a solid-solution equilibrium process. Furthermore, PSE can be performed at room temperature, allowing the incorporation of thermally unstable ligands into MOFs. In this work, we demonstrate the practicality of PSE by using heterocyclic triazole- and tetrazole-containing ligands to functionalize a Zr-based MOF (UiO-66; UiO = University of Oslo). After digestion, the functionalized MOFs are characterized via various techniques, including powder X-ray diffraction and nuclear magnetic resonance spectroscopy.

作者聚焦：金属有机框架功能化：合成后配体交换的进步、挑战和力量 

Post-synthetic ligand exchange (PSE) is a versatile and powerful tool for installing functional groups into metal-organic frameworks (MOFs). Exposing MOFs to solutions containing triazole- and tetrazole-functionalized ligands can incorporate these heterocyclic moieties into Zr-MOFs through PSE processes.

通过合成后配体交换合成三唑和四唑功能化Zr基金属有机骨架

Metal-organic frameworks (MOFs) are a class of porous materials that are formed through coordination bonds between metal clusters and organic ligands. ...

一个水溶性金属 - 有机络合物阵列合成

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功能化的合成与表征金属 - 有机骨架

的合成[锡

半导体回转金属硫框架结晶的硫醇构建块的合成

金属-有机框架的表面功能化改善防潮性能

单晶核壳金属有机骨架的合成

多位膦接头合成低价金属有机骨架的实验方法

多位膦接头合成低价金属有机骨架的实验方法

多位膦接头合成低价金属有机骨架的实验方法

通过合成后配体交换合成三唑和四唑功能化Zr基金属有机骨架

通过合成后配体交换合成三唑和四唑功能化Zr基金属有机骨架