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Chemistry

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

Published: June 23, 2023
doi:
10.3791/65619
, , ,
1Department of Chemistry,Chungbuk National University, 2Department of Chemistry Education,Seoul National University

Summary

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。

Abstract

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。

Introduction

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。

Figure 1
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。 请点击此处查看此图的大图。

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。

Protocol

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 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 。 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</stro…

Representative Results

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…

Discussion

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?…

Disclosures

The authors have nothing to disclose.

Acknowledgements

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。

Materials

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

Keywords: Metal-organic FrameworksMOFsPost-synthetic Ligand ExchangePSETriazoleTetrazoleFunctionalizationZr-based MOFsUiO-66
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Lee, S., Lee, D., Kim, J. Y., Kim, M. Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange. J. Vis. Exp. (196), e65619, doi:10.3791/65619 (2023).
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