这项研究得到了科学和信息通信技术部资助的韩国国家研究基金会（NRF）（NRF-2022R1A2C1009706）的基础科学研究计划的支持。

制备MOF和配体所需的试剂列在 材料表中。
1. 建立合成后配体交换（PSE）过程
<ol><li>在真空下完全干燥预合成的UiO-66 MOF，以去除孔隙中任何未反应的金属盐和配体，以及残留的溶剂残留物过夜。 注：UiO-66 MOF的合成程序见 补充文件1 。</li>
	<li>制备功能化配体，H 2 BDC-三唑和H2BDC-四氮唑（制备过程见补充文件1;补充图1和补充图2用于表征）在隔离状态下并在真空下完全干燥过夜。</li>
	<li>通过将氢氧化钾溶解在去离子水中来制备4%氢氧化钾（KOH）水溶液。</li>
	<li>在带聚丙烯（PP）盖的20 mL闪烁瓶中进行PSE过程（参见 材料表）。</li>
	<li>测量H 2 BDC-三唑（23.3mg，0.1mmol）或H2BDC-四唑（23.4mg，0.1mmol）并放入闪烁瓶中。</li>
	<li>将H2BDC配体溶解在水溶液中。使用玻璃移液管将 1.0 mL 的 4% KOH 水溶液转移到含有 BDC-三唑或 BDC-四唑的闪烁瓶中。 注意：4%KOH水溶液是高度碱性的。避免任何形式的接触，并穿戴个人防护装备。</li>
	<li>超声处理混合物，直到所有固体完全溶解。</li>
	<li>将溶液中和至pH 7。使用玻璃移液管将1 M盐酸（HCl）水溶液搅拌转移到含有二羧酸的闪烁瓶中，直到达到pH 7。通过pH纸（及其颜色）或pH计测量pH值。 注意：在交换过程中保持pH值为7至关重要，因为MOF在碱性条件下（>pH 7）通常不稳定，并且BDC配体在酸性条件下（<pH 7）不溶。大约需要 1.5 mL 的 1 M HCl 水溶液来中和 BDC-三唑或含 BDC-四唑的溶液。</li>
	<li>将MOF加入二羧酸盐溶液中并孵育。将UiO-66 MOF（33mg，0.02mmol）加入含有pH 7溶液的闪烁瓶中。 注意：在pH 7时，UiO-66 MOF颗粒不溶于水，导致它们悬浮在水中。</li>
	<li>将含有MOF和配体的闪烁瓶在摇床中以120rpm和室温孵育24小时。 注意：搅拌可用作PSE工艺摇床孵育的替代方案。但是，应谨慎行事，因为磁力搅拌棒和MOF之间的物理接触会导致MOF颗粒破裂或断裂。</li>
</ol>2. 隔离交换的MOF和洗涤过程
<ol><li>孵育后，通过离心（1,166 x g ，5 分钟，室温）从混合物中分离固体 MOF。</li>
	<li>向获得的固体MOF中加入新鲜甲醇（10mL）并摇动混合物以形成非均相混合物以溶解剩余的未交换BDC配体。</li>
	<li>分离通过离心分离的固体（1,166 x g ，5分钟，室温）。</li>
	<li>再重复步骤2.2-2.3两次，总共三个洗涤周期。</li>
	<li>最后一次洗涤后，在真空下将交换的MOF固体完全干燥过夜。</li>
</ol>3. 粉末X射线衍射（PXRD）表征MOF的
<ol><li>将大约 10 mg 交换的 MOF 固体转移到 PXRD 样品架上（参见 材料表）。</li>
	<li>将样品架放入衍射仪中。</li>
	<li>收集 5° 至 30° 2θ 范围内的 PXRD 图型（图 2）。</li>
	<li>将获得的数据与父UiO-66 MOF和模拟模式进行比较。</li>
</ol>4. 消化后核磁共振（NMR）表征MOF
<ol><li>将大约 30 mg 交换的 MOF 固体转移到新鲜的 4 mL 小瓶中。</li>
	<li>使用微量移液器将 400 μL DMSO-d 6 转移到 MOF 样品中。</li>
	<li>使用微量移液器将 200 μL 4.14 M NH4F/D2O 溶液转移到 MOF 粉末的 DMSO-d 6 悬浮液中。 注意：可以使用大约 40% HF 的水溶液代替 NH4F/D2O 溶液。在这种情况下，在NMR中观察到一个显着的H2O峰。然而，在HF消解的情况下，可以更清晰的消化。 注意：HF对身体和中枢神经系统有剧毒。应避免所有形式的接触，应在通风橱中进行工作，并应穿戴个人防护设备。</li>
	<li>超声处理非均相混合物30分钟，直到MOF在消化后溶解在二甲基亚砜（DMSO）-D2O混合溶剂中。</li>
	<li>通过聚偏二氟乙烯（PVDF）注射器过滤器（Φ 13 mm，0.45 μm孔;参见 材料表）过滤溶液，同时将其从4 mL小瓶转移到NMR管中，从而去除任何剩余的不溶性固体。</li>
	<li>将核磁共振管放入核磁共振机器中。收集核磁共振数据（图3）。</li>
</ol>

三唑和四唑官能化 Zr-MOF 的合成和表征

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作者没有什么可透露的。

具有功能化BDC配体的PSE过程对Zr基UiO-66 MOF是一种简单而通用的获得带有化学标签的MOF的方法。PSE工艺最好在水性介质中进行，需要将配体溶解在水性介质中的初始步骤。当使用带有官能团的预合成BDC时，建议直接溶解在碱性溶剂中，例如4%KOH水溶液。或者，可以使用苯-1,4-二羧酸钠盐或钾盐。中和至pH 7对于使用功能化BDC的PSE工艺至关重要，因为MOFs在碱性条件下的低稳定性可能导致功效降低。建议?...

金属有机骨架（MOFs）是通过金属簇和多主题有机配体之间的配位键形成的三维多孔材料。MOF因其永久孔隙率、低密度以及结合有机和无机组分的能力而受到广泛关注，这使得多样化的应用成为可能1,2。此外，广泛的金属节点和支柱有机接头为MOF提供了理论上无限的结构组合。即使具有相同的框架结构，MOFs的物理和化学性质也可以通过配体功能化与化学标签来改变。这种改性过程为针对特定应用定制MOF的性质提供了一条有希望的途径3,4,5,6,7,8,9。
MOF合成前配体的预官能化和MOF的合成后修饰（PSM）都被用于引入和/或修饰MOF配体10,11中的官能团。特别是，共价PSMs已被广泛研究以引入新的官能团并产生一系列具有不同官能团的MOFs12,13,14。例如，UiO-66-NH2可以通过与适当的酰基卤（如乙酰氯或正己酰氯）的酰化反应转化为具有不同链长（从最短的乙酰胺到最长的正己基酰胺）的酰胺官能化UiO-66-AMs15,16。该方法证明了共价PSM将特定官能团引入MOF配体的多功能性，为广泛的应用铺平了道路。
除了共价PSM，合成后配体交换（PSE）是修饰MOF的一种有前途的策略（图1）。由于MOF由金属和配体（例如羧酸盐）之间的配位键组成，因此这些配位键可以用溶液中的外部配体代替。 将MOF暴露于含有具有化学标签的所需配体的溶液中可以通过PSE 17,18,19,20,21,22掺入MOF中。由于配位溶剂的存在加速了PSE过程，因此这种现象也称为溶剂辅助配体交换（SALE）23,24。该方法提供了一种灵活而简便的方法，用于使用广泛的外部配体功能化MOF，从而实现广泛的应用25,26,27,28,29。
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/65619/65619fig01.jpg"> 图 1：通过 PSE 合成三唑和四唑官能化的 H2BDC 配体以及制备三唑和四唑官能化的 UiO-66 MOF。 <a href="https://www.jove.com/files/ftp_upload/65619/65619fig01large.jpg" target="_blank">请点击此处查看此图的大图。</a>
PSE过程的进度可以通过调整配体比，交换温度和时间来控制。值得注意的是，室温PSE可以通过将溶液中的配体交换为MOF固体20来获得功能化的MOF。PSE策略对于将热不稳定官能团（如叠氮基团）和配位官能团（如苯酚基团）引入MOF结构特别有用18。此外，PSE策略已应用于具有金属和配位键变化的各种MOF。这种交换是MOFs 30,31,32化学中的通用过程。在这项研究中，我们提出了PSE从原始，非功能化MOF中获取功能化MOF的详细协议，并提供了一种表征策略来确认MOFs的成功功能化。该方法证明了PSE修饰不同官能团MOF的通用性和便利性。
合成含四唑的苯-1,4-二羧酸（H 2 BDC-四唑）33和含三唑的苯-1,4-二羧酸（H2BDC-三唑）作为靶配体，用于UiO-66 MOF的PSE，以获得新型、无配位的含三唑的MOF。三唑和四唑在其杂环上都具有酸性N-H质子，并且可以与金属阳离子配位，因此它们可用于构建MOFs 34,35。然而，关于将无配位的四唑类和三唑类药物纳入MOF和相关结构的研究有限。在三唑官能化Zr-MOFs的情况下，通过具有苯并三唑官能度的直接溶剂热合成研究了UiO-68型MOFs的光物理性质36。对于四唑功能化的Zr-MOFs，采用混合直接合成33。这些杂环功能化的MOFs可以在MOF孔中提供潜在的协调位点，用于催化，通过结合亲和力选择性分子摄取以及与能量相关的应用，例如燃料电池中的质子传导。

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>2-Bromoterephthalic acid</td>
			<td>BLD Pharm</td>
			<td>BD5695</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Azidotrimethylsilane</td>
			<td>Simga Aldrich</td>
			<td>155071</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Bis(triphenylphosphine)palladium(II) dichloride</td>
			<td>TCI</td>
			<td>B1667</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Copper(I) cyanide</td>
			<td>Alfa-Aesar</td>
			<td>12135</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Copper(I) iodide</td>
			<td>Acros organics</td>
			<td>20150</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Digital Orbital Shaker</td>
			<td>Daihan Scientific</td>
			<td>SHO-1D</td>
			<td>PSE</td>
		</tr>
		<tr>
			<td>Formic Acid</td>
			<td>Daejung chemical</td>
			<td>F0195</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Hybrid LC/Q-TOF system</td>
			<td>Bruker BioSciences</td>
			<td>maXis 4G</td>
			<td>HR-MS</td>
		</tr>
		<tr>
			<td>Lithum hydroxide monohydrate</td>
			<td>Daejung chemical</td>
			<td>5087-4405</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Magnesium sulfate</td>
			<td>Samchun chemical</td>
			<td>M1807</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Methyl alcohol</td>
			<td>Daejung chemical</td>
			<td>M0584</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>N,N-Dimethylformamide</td>
			<td>Daejung chemical</td>
			<td>D0552</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Nuclear Magnetic Resonance Spectrometer-500 MHz</td>
			<td>Bruker</td>
			<td>AVANCE 500MHz</td>
			<td>NMR</td>
		</tr>
		<tr>
			<td>Polypropylene cap (22 mm, Cork-Backed Foil Lined)</td>
			<td>Sungho Korea</td>
			<td>22-200</td>
			<td>material for digestion</td>
		</tr>
		<tr>
			<td>Potassium cyanide</td>
			<td>Alfa-Aesar</td>
			<td>L13273</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>PVDF Synringe filter (13 mm, 0.45 &#181;m)</td>
			<td>LK Lab Korea</td>
			<td>F14-61-363</td>
			<td>material for digestion</td>
		</tr>
		<tr>
			<td>Scintillation vial (20 mL, borosilicate glass)</td>
			<td>Sungho Korea</td>
			<td>74504-20</td>
			<td>material for digestion</td>
		</tr>
		<tr>
			<td>Sodium azide&#160;</td>
			<td>TCI</td>
			<td>S0489</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Sodium bicarbonate</td>
			<td>Samchun chemical</td>
			<td>S0343</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Tetrabutylammonium fluoride (1 M THF solution)</td>
			<td>Acros organics</td>
			<td>20195</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Triethylamine</td>
			<td>TCI</td>
			<td>T0424</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Triethylamine hydrochloride</td>
			<td>Daejung chemical</td>
			<td>8628-4405</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Trimethylsilyl-acetylene</td>
			<td>Alfa-Aesar</td>
			<td>A12856</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Triphenylphosphine</td>
			<td>TCI</td>
			<td>T0519</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>X RAY DIFFRACTOMETER SYSTEM</td>
			<td>Rigaku</td>
			<td>MiniFlex 600</td>
			<td>PXRD</td>
		</tr>
		<tr>
			<td>Zirconium(IV) chloride</td>
			<td>Alfa-Aesar</td>
			<td>12104</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
	</tbody>
</table>

synthesis of triazole and tetrazole-functionalized zr-based metal-organic frameworks through post-synthetic ligand exchange

金属有机骨架（MOF）是通过金属簇和有机配体之间的配位键形成的一类多孔材料。鉴于它们的配位性质，有机配体和支柱框架可以很容易地从MOF中去除和/或与其他配位分子交换。通过将靶配体引入含MOF的溶液中，可以通过称为合成后配体交换（PSE）的过程 获得 具有新化学标签的功能化MOF。PSE是一种简单实用的方法，可通过固溶平衡过程 制备 具有新化学标签的各种MOF。此外，PSE可以在室温下进行，允许将热不稳定的配体掺入MOF中。在这项工作中，我们通过使用含杂环三唑和四唑的配体来官能化基于Zr的MOF（UiO-66;UiO = 奥斯陆大学）。消解后，通过粉末X射线衍射和核磁共振波谱等多种技术 对 功能化的MOF进行表征。

Metal-organic frameworks (MOFs) are three-dimensional porous materials that are formed through coordination bonds between metal clusters and multi-topic organic ligands. MOFs have garnered significant attention due to their permanent porosity, low density, and ability to associate organic and inorganic components, which enables diverse applications1,2. Moreover, the vast range of metal nodes and strut organic linkers offer MOFs theoretically unlimited structural combinations. Even with identical framework structures, MOFs&#39; physical and chemical properties can be modified through ligand functionalization with chemical tags. This modification process offers a promising route to tailor the properties of MOFs for specific applications3,4,5,6,7,8,9.
Both the pre-functionalization of ligands prior to MOF synthesis and post-synthetic modification (PSM) of MOFs have been employed to introduce and/or modify functional groups in MOF ligands10,11. In particular, covalent PSMs have been extensively studied to introduce new functional groups and generate a range of MOFs with diverse functionalities12,13,14. For instance, UiO-66-NH2 can be converted to amide-functionalized UiO-66-AMs with different chain lengths (ranging from the shortest acetamide to the longest n-hexyl amide) through acylation reactions with appropriate acyl halides (such as acetyl chloride or n-hexanoyl chloride)15,16. This approach demonstrates the versatility of covalent PSMs to introduce specific functional groups onto MOF ligands, paving the way for a broad range of applications.
In addition to covalent PSMs, post-synthetic ligand exchange (PSE) is a promising strategy for modifying MOFs (Figure 1). Since MOFs are composed of coordination bonds between metals and ligands (such as carboxylates), these coordination bonds can be replaced with external ligands from a solution. Exposing MOFs to a solution containing the desired ligand with chemical tags can be incorporated into the MOFs via PSE17,18,19,20,21,22. Since the PSE process is accelerated by the existence of coordinative solvents, the phenomenon is also called solvent-assisted ligand exchange (SALE)23,24. This approach offers a flexible and facile method for functionalizing MOFs with a wide range of external ligands, enabling a broad spectrum of applications25,26,27,28,29.
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/65619/65619fig01.jpg" /> 
Figure 1: Synthesis of triazole and tetrazole-functionalized H2BDC ligands and preparation of triazole- and tetrazole-functionalized UiO-66 MOF through PSE. <a href="https://www.jove.com/files/ftp_upload/65619/65619fig01large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
The progress of the PSE process can be controlled by adjusting the ligand ratio, exchange temperature, and time. Notably, room temperature PSE can be employed to obtain functionalized MOFs by exchanging ligands from a solution into MOF solids20. The PSE strategy is particularly useful for introducing both thermally unstable functional groups (such as azido groups) and coordinative functional groups (such as phenol groups) into MOF structures18. In addition, the PSE strategy has been applied to various MOFs with metal and coordination bond variations. This exchange is a universal process in the chemistry of MOFs30,31,32. In this study, we present a detailed protocol for PSE to obtain functionalized MOFs from pristine, non-functionalized MOFs, and we provide a characterization strategy to confirm successful functionalization of the MOFs. This method demonstrates the versatility and convenience of PSE for modifying MOFs with diverse functional groups.
Tetrazole-containing benzene-1,4-dicarboxylic acid (H2BDC-Tetrazole)33, and triazole-containing benzene-1,4-dicarboxylic acid (H2BDC-Triazole) are synthesized as target ligands and utilized in the PSE of UiO-66 MOFs to obtain novel, coordination-free, triazole-containing MOFs. Both triazoles and tetrazoles possess acidic N-H protons on their heterocyclic rings and can coordinate with metal cations, thus enabling their use in constructing MOFs34,35. However, there are limited studies on incorporating coordination-free tetrazoles and triazoles into MOFs and related structures. In case of triazole-functionalized Zr-MOFs, UiO-68 type MOFs were investigated to photophysical properties through direct solvothermal synthesis with benzotriazole functionalities36. For tetrazole-functionalized Zr-MOFs, the mixed direct synthesis was employed33. These heterocycle-functionalized MOFs could provide potential coordinating sites in MOF pores for catalysis, selective molecular uptake by binding affinity, and energy-related applications, such as proton conduction in fuel cells.

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 

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

交换的UiO-66 MOF、UiO-66-三唑和UiO-66-四氮唑的成功合成产生了无色微晶固体。H 2 BDC-三唑和H2BDC-四唑配体也表现出无色固态。用于确定交换成功的标准方法包括测量PXRD图案并将样品的结晶度与原始UiO-66 MOF进行比较。图2显示了交换的UiO-66-三唑和UiO-66-四唑的PXRD模式，以及原始UiO-66和模拟数据。模拟的PXRD图谱是根据所报道的目标MOF的晶体结构生成的。由于配体交...

Watch this Scientific Journal Video about Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange at JoVE.com

合成后配体交换（PSE）是一种多功能且功能强大的工具，用于将官能团安装到金属有机框架（MOF）中。将MOF暴露于含有三唑和四唑官能化配体的溶液中，可以通过PSE工艺将这些杂环部分掺入Zr-MOF中。

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

我们的主要研究课题是通过各种技术将具有有趣官能团的多孔金属有机框架MOFs功能化。本研究的重点是MOF中的杂轮安装。PSE，合成后配体交换是这项工作的主要技术。在整个固溶体交换过程中，具有目标官能团的配体可以安装在预合成的MOFS中。特别是， 一些不稳定的配体和具有配位基团的配体可以通过PSE技术有效地掺入MOFs中.三唑和四唑官能团都具有多个配位氮槽。因此，金属羧酸盐与金属三唑酸盐或四唑酸盐之间存在协调竞争。在PSE过程中，靶配体的掺入比例很容易控制，并且通过这种方法可以在单个MOF中安装多个靶标。

synthesis-triazole-tetrazole-functionalized-zr-based-metal-organic

Research

JoVE Journal

Chemistry

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

1.9K 次观看.  Chungbuk National University. 我们的主要研究课题是通过各种技术将具有有趣官能团的多孔金属有机框架MOFs功能化。本研究的重点是MOF中的杂轮安装。PSE，合成后配体交换是这项工作的主要技术。在整个固溶体交换过程中，具有目标官能团的配体可以安装在预合成的MOFS中。特别是， 一些不稳定的配体和具有配位基团的配体可以通过PSE技术有效地掺入MOFs中.三唑和四唑官能团都具有多个配位氮槽。

视频: 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 

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.

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.