SuFEx in MetalâOrganic Frameworks: Versatile Postsynthetic

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SuFEx in Metal-Organic Frameworks: a Versatile Post-synthetic Modification Tool Seungjae Park, Hayoung Song, Nakeun Ko, Changhee Kim, Kimoon Kim, and Eunsung Lee ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b14065 • Publication Date (Web): 19 Sep 2018 Downloaded from http://pubs.acs.org on September 20, 2018

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ACS Applied Materials & Interfaces

SuFEx in Metal-Organic Frameworks: a Versatile Postsynthetic Modification Tool Seungjae Park,†,‡,∥ Hayoung Song,†,‡,∥ Nakeun Ko,†,‡ Changhee Kim,§ Kimoon Kim,*,†,‡ and Eunsung Lee*,†,‡,# †

Center for Self–assembly and Complexity, Institute for Basic Science (IBS), Pohang, 790–784, Republic of Korea Department of Chemistry, Pohang University of Science and Technology, Pohang, 790–784, Republic of Korea # Division of Advanced Materials Science, Pohang University of Science and Technology, Pohang, 790–784, Republic of Korea § Department of Chemistry, College of Natural Science, Seoul National University, Seoul 440-746, Republic of Korea ‡

KEYWORDS. metal-organic frameworks, post-synthetic modification, SuFEx chemistry, click chemistry, heterogeneous catalysis

Supporting Information Placeholder ABSTRACT: A new type of click reaction, sulfur(VI) fluoride exchange (SuFEx), has been utilized to prepare five post-synthetically modified UiO-67 series metal-organic frameworks (MOFs). The post-synthetic modification (PSM) via SuFEx can be achieved selectively for the sulfonyl fluoride (R-SO2F) without degrading the MOF structure as confirmed by X-ray crystallographic analysis. The present SuFEx method provides a straightforward tool for introducing new functionality inside MOFs. Introduction of imidazolium group into the MOF afforded a heterogeneous catalyst for the benzoin condensation reaction. Metal-organic frameworks (MOFs) are representative porous remained Cu(I) catalyst in modified MOFs by CuAAC, the Cu(I)crystalline materials consisting of metals and organic linkers.1 As free PSMs of MOFs were also attempted to overcome the the interest in applications of MOFs such as gas storage and contamination problem,38 such as strained-promoted click 2, 3 4 5 6, 7 separation, reaction39, 40 using cyclooctyne substrates, coordinated azidesensing, electrical conductivity, and catalysis has increased, the efficient introduction of desired functionality alkyne click reaction of Mn-MOFs,41 and 1,3-dipolar nitrile oxideinto MOFs has received much attention to afford MOFs with alkyne cycloaddition.38 improved properties. Among the MOF functionalization methods, Scheme 1. Sulfur(VI) Fluoride Exchange (SuFEx) Reacpost-synthetic modification (PSM) has received the spotlight as an tions. 8-10 elegant functionalization method. The introduction of O O O O no cat. functional groups in MOF, which had many limitations with + FG + R3 SiF S O S Ar or FG SiR 3 O Ar F existing direct synthesis, could be easily made possible by cat. DBU PSMs.11, 12 PSMs developed by Lee,13 Kim,14, 15 Cohen,16-19 RR FG Yaghi,20, 21 and many other researchers enable existing MOFs to O Si R be applied to numerous applications by functionalization of the Ar S F open frameworks. Recently, the post-synthetically modified O O MOFs with biomolecules were also applied as a platform to 22 Herein, we report a new PSM strategy based on the newly donate enzyme-like complexity. developed "sulfur(VI) fluoride exchange (SuFEx)" by Sharpless et For versatile applicability of these methods, the copper(I)al.42-50 SuFEx is a new generation of click reaction that substitutes catalyzed azide-alkyne cycloaddition reaction (CuAAC),23, 24 the a fluorine atom with a desirable functional group by the aid of the archetypal “click reaction”, has been applied to the 25 strong Si−F bond when the functional group with tertfunctionalization of MOFs. After synthesis of azide- or alkynebutyldimethylsilyl (TBDMS)-ether or TBDMS-amine is treated in functionalized MOFs, the counterparts of the alkyne or azide the presence of R–SO2F (Scheme 1). This reaction can be carried substrates are introduced into the MOFs via CuAAC.26-37 This out with catalysts such as 1,8-diazabicyclo[5.4.0]undec-7-ene approach has been further developed for one-pot two-step click reaction based on the amine-to-azide transformation of amineMOFs.27 Nevertheless, due to the potential concern of the

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SO2F O SO2F

HO

ZrCl4 OH O

L-SO2F

PhCO2H 120 oC, 48 h DMF

UiO-67-SO2F (1)

Si O

MeOTMS

MeCN 85 oC, 48 h - TMSF

UiO-67-SO3Me (2)

Br N

N

O

Si


[R1-OTMS]Br

UiO-67-SO3R1Br (3)

O

N O

Si

R2 -OTMS


Si

N H

Si

R3-NHTMS

UiO-67-SO3R2 (4)


UiO-67-SO2NHR3 (5)

TMSO

OH NHBoc


R4-OTMS

UiO-67-SO3R4 (6)

Figure 1. Post-synthetic modification of UiO-67-SO2F (1) via SuFEx and single crystal X-ray structures of extended framework of UiO67-SO2F and its modified UiO-67s. For details on the X-ray structures, see the Supporting Information. (DBU)42 or bifluoride salts.51 This method has several advantages: (a) The S(VI)–F bond is stable (80-90 kcal/mol) under typical oxidation or high temperature (up to 230 °C) conditions, (b) the only byproduct, highly stable silyl fluoride can be easily removed by simple washing or vaporization, and (c) the sulfonyl fluoride and silyl substrates used in the reaction are easily prepared compared with other clickable functional groups such as azide and alkyne groups. We have successfully synthesized UiO-67-SO2F (1) from a sulfonyl fluoride linker; to the best of our knowledge, this is the first time it has been prepared. Furthermore, the postsynthetic modification of 1 using five trimethylsilyl (TMS)-ether and TMS-amine substrates has been successfully demonstrated without any catalyst, even in the crystalline products with full characterization by single crystal X-ray diffraction analysis. Based on the method developed by Sharpless et al., the sulfonyl fluoride ligand (2-(fluorosulfonyl)-[1,1'-biphenyl]-4,4'dicarboxylic acid, L-SO2F; Figure 1) was prepared by the fluorination of 4,4'-dimethyl-1,1'-biphenyl-2-sulfonyl chloride with KHF2 in biphasic THF/H2O solution, followed by the oxidation of the methyl group of biphenyl using CrO3 in acetic acid (see SupFigure 2. The powder X-ray diffraction (PXRD) pattern of UiOporting Information). Consistent with the previous results,42 it was 67-SO2F (1), UiO-67-SO3Me (2), UiO-67-SO3R1Br (3), UiO-67confirmed that the SO2F group was stable even under the strong SO 3R2 (4), UiO-67-SO2NHR3 (5), and UiO-67-SO3R4 (6). acidic and oxidative conditions. To secure the high thermal and The powder X-ray diffraction (PXRD) pattern of 1 was also chemical stability of MOF, we have synthesized the zirconiumconsistent with the simulated pattern generated from its single based MOF (UiO-67),52 as PSM of UiO series has been extensivecrystal X-ray structure (Figure 2). The crystallinity of 1 was mainly studied for the past decade.19, 53-55 Using the well-known additained, as evidenced by PXRD and thermogravimetric analysis tive effect of benzoic acid,56 1 was successfully prepared as octa(TGA) data even after heating the crystals of 1 up to 350 °C (Fighedron-shaped crystals by the solvothermal reaction of ZrCl4, Lure S3). The gas sorption experiment with N2 at 77 K clearly SO2F, and benzoic acid in N,N-dimethylformamide (DMF) at demonstrated that 1 shows the same isotherm I as its parent, UiO120 °C for 48 h (Figure 1). The structure of 1 was confirmed by a 67. The Brunauer-Emmett-Teller (BET) surface area of 1 was single crystal X-ray diffraction (SXRD) study. 1, which crystalmeasured to afford 1572 m2 g-1 (Figure 3). The smaller surface lized in Fm-3m space group, consists of tetrahedral and octahedral area of 1 than that of the parent UiO-67 was due to the presence cages with an fcu topology (Figure 1). of the bulky sulfonyl fluoride group in the linker.


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Figure 3. The gas adsorption (open symbols) and desorption (closed symbols) isotherms of UiO-67-SO2F (1), UiO-67-SO3Me (2), UiO-67-SO3R1Br (3), UiO-67-SO3R2 (4), UiO-67-SO2NHR3 (5), and UiO-67-SO3R4 (6) with N2 at 77 K. To achieve SuFEx-based PSM from 1, we treated methoxytrimethylsilane (TMS–OMe), 1-methyl-3-(2(trimethylsilyloxy)ethyl)-1H-imidazolium bromide ([TMSO−R1]Br), 2-((trimethylsilyl)oxy)pyridine (TMSO−R2), bis(trimethylsilyl)amine (TMS−NHR3), and 2-((tertbutoxycarbonyl)amino)-3-((trimethylsilyl)oxy)propanoic acid (NBoc-O-TMS-L-serine, TMSO−R4) as PSM partners of 1 in MeCN (Figure 1 and see Supporting Information) to produce UiO-67SO3Me (2), UiO-67-SO3R1Br (3), UiO-67-SO3R2 (4), UiO-67SO2NHR3 (5), and UiO-67-SO3R4 (6), respectively. The silylated compounds were prepared within 2 steps by the silylation in good yields (See the SI).

firmed by 19F-NMR spectroscopy. Finally, the reaction was completed within 48 h without the base catalyst. The PXRD patterns of five post-synthetically modified MOFs were also retained compared to 1 (Figure 2). Furthermore, single crystals of 1 were converted into the functionalized MOFs without losing single crystallinity confirming that the SuFEx-based PSM can be carried out. The SuFEx-PSM of 1 was also confirmed by the SXRD studies of the products (Figure 1). The postsynthetically modified MOFs were digested with a 50% aqueous HF and subsequently the solution was analyzed by 1H-NMR spectroscopy to confirm that the SuFEx-based PSM was successfully carried out as the fluoride of the ligand was replaced (Figure S7, S8, S9, S10, and S11). According to the digestion analysis, conversion yields of 2, 3, 4, 5, and 6 were 85%, 99%, 99%, 84%, and 63%, respectively. Furthermore, the only byproduct, TMS–F, could be removed during simple washing and drying under vacuum at room temperature (Figure S7, S8, S9, S10, and S11). The gas sorption experiment with N2 at 77 K was carried out to evaluate the porosity of post-synthetically modified MOFs after the SuFEx-based PSM. The BET surface areas of 2, 3, 4, 5, and 6 were decreased to 1510, 1077, 1311, 1556, and 1044 m2 g-1, respectively corresponding to the conversion yields and the bulkier substituents rather than fluoride (Figure 3). Furthermore, according to the gas sorption experiment, it showed the porous structures were also well retained after SuFEx. Among various applications of imidazolium functionalized MOFs such as proton conductivities,57, 58 post-synthetic transitionmetal complexation,21 and catalysis,59, 60 examples of organocatalysis using imidazolium functionalized MOFs as N-heterocyclic carbene (NHC) catalysts are rare.61, 62 Thus, we decided to explore the use of 3 as a heterogeneous catalyst for the benzoin condensation reaction (Table 1). Before the reaction, 3 was activated by treatment with potassium tert-butoxide (KOtBu) as a base for 30 min. The activated 3 successfully catalyzed the transformation of benzaldehyde to benzoin while its crystallinity was retained after the catalysis (Table 1, entry 3, and Figure S2). However, 1 did not show any conversion of benzaldehyde to benzoin under the same reaction conditions. Interestingly, the in situ generation of free NHC from HOR1Br did not show full conversion of benzaldehyde (Table 1, entry 2), as the free NHC generated from HOR1Br easily decomposes and loses its catalytic activity presumably due to its pendent hydroxyl functional group. The recyclability of 3 as a heterogeneous catalyst was also confirmed (entry 4). Table 1. Benzoin condensation using UiO-67-SO3R1Br (3). O

O

Condition H THF, rt, 1 d Enrty

Condition (equiv)

Yielda

1

UiO-67-SO2F (0.1), KOt Bu (0.1)

0%

t

2

Figure 4. The reaction monitoring of SuFEx with TMSOR1Br in (a) 1H-NMR/CD3CN and (b) 19F-NMR/CD3CN. We confirmed the SuFEx in MOFs with the generation of trimethylsilylfluoride (TMS–F) by 1H- and 19F-NMR spectroscopy (Figure 4, S5, and S6). As the reaction proceeds, the small 1HNMR signals corresponding to TMS–F appear at the room temperature after 3 h. When the reaction temperature was raised up to 50 °C to push the SuFEx reaction, the doublet peak at 0.21 ppm of TMS–F was increased in 1H-NMR spectroscopy. In addition, the singlet peak at ‒157 ppm corresponding to TMS–F was also con-

OH

3

HOR1Br (0.1), KO Bu (0.1) UiO-67-SO3R1Br (0.1), KO Bu (0.1)

4 a

t

2nd

/

3r d

cycle

75 % 99 % 99 %

1

The yield was determined by H NMR.

In summary, we have demonstrated that the new type of click reaction, SuFEx, can be employed a versatile tool for PSM of MOFs. To illustrate the principle, a UiO-67 type MOF with a sulfonyl fluoride group was successfully synthesized for the first time. Various functional groups were introduced into the MOF via SuFEx, which has been characterized by various analytical methods. Furthermore, the PSM can be achieved selectively for



the sulfonyl fluoride (R-SO2F) without degrading the MOF structure as confirmed by single crystal X-ray diffraction methods. We believe that the present platform, SuFExable MOF, provides a new route to introduce useful functional groups inside MOFs by PSM. In particular, natural compounds with hydroxyl or amine groups, such as amino acids, sugars, and proteins, can be introduced into this platform via SuFEx click chemistry. Furthermore, this SuFEx-based PSMs can be extended to other MOFs. Work along this line is in progress.

ASSOCIATED CONTENT Supporting Information Detailed experimental procedures, spectroscopic data for all new compounds, crystallographic data (CIF). This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author [email protected] [email protected]

Author Contributions ∥

S. P. and H. S. contributed equally.

Notes A patent application has been ﬁled through POSTECH and IBS on reagents presented in this manuscript

ACKNOWLEDGMENT This work was supported by Institute for Basic Science (IBS) [IBSR007-D1]. The X-ray crystallography analysis with synchrotron radiation was performed at the Pohang Accelerator Laboratory (PLS-II BL 2D SMC and 6D C&S Unist-PAL beamline). National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP: Ministry of Science, ICT and Future Planning) (No. NRF-2017H1A2A1046576, 2016H1A2A1907122 - Global Ph.D. Fellowship Program). We thank Dr. James Murray for helpful suggestions in preparation of the manuscript.

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