Covalent surface modification of a metal–organic framework: selective surface engineering via CuI-catalyzed Huisgen cycloaddition

Gadzikwa, Tendai; Lü, Guang; Stern, Charlotte L.; Wilson, Scott R.; Hupp, Joseph T.; Nguyen, SonBinh T.

doi:10.1039/b805101a

Cited by 158 publications

(107 citation statements)

References 23 publications

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“…Most of the previous studies on MOF postsynthetic modification have shown the introduction of only a single chemical modification into the MOF lattice. Very few have demonstrated that more than one chemical reagent could be used to covalently modify a single MOF structure 45,58. In one example, two different anhydrides were used to successfully modify isoreticular metal-organic frame-work-3 (IRMOF-3, Chart 1).…”

Section: Introductionmentioning

confidence: 99%

Postsynthetic Modification: A Versatile Approach Toward Multifunctional Metal-Organic Frameworks

et al. 2009

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An isoreticular metal-organic framework (IRMOF-3) containing 2-amino-1,4-benzenedicarboxylic acid (NH2–BDC) as a building block is shown to undergo chemical modification with a diverse series of anhydrides and isocyanates. The modification of IRMOF-3 by these reagents has been evidenced by using a variety of methods, including NMR and electrospray ionization mass spectrometry, and the structural integrity of the modified MOFs has been confirmed by thermogravimetric analysis, powder X-ray diffraction, and gas sorption analysis. The results show that a variety of functional groups can be introduced onto the MOF including amines, carboxylic acids, and chiral groups. Furthermore, it is shown that tert-butyl-based asymmetric anhydrides can be used to selectively deliver chemical payloads to the IRMOF. Finally, the results demonstrate that at least four different chemical modifications can be performed on IRMOF-3 and that the reaction conditions can be modulated to control the relative abundance of each group. The findings presented here demonstrate several important features of postsynthetic modification on IRMOF-3, including (1) facile introduction of a wide range of functional groups using simple reagents (e.g., anhydrides and isocyanates), (2) the introduction of multiple (as many as four different) substituents into the MOF lattice, and (3) control over reaction conditions to preserve the crystallinity and microporosity of the resultant MOFs. The findings clearly illustrate that postsynthetic modification represents a powerful means to access new MOF compounds with unprecedented chemical complexity, which may serve as the basis of multifunctional materials.

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Section: Introductionmentioning

confidence: 99%

Postsynthetic Modification: A Versatile Approach Toward Multifunctional Metal-Organic Frameworks

et al. 2009

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“…The XPS results clearly show the difference in binding energies from azide (a) to the product triazole (b), where no residual azide was detected. The absence of azide nitrogens thus shows that the reaction has proceeded, though it cannot be unambiguously concluded that all azides have reacted to form Beside the above mentioned techniques some of the other techniques that are used for characterizing surface modification of materials are matrix assisted laser desorption/ionization-time of flight (MALDI-TOF), [66,67] size-exclusion chromatography (SEC), [68] cyclic voltammetry, [69] contact angle measurement, [70] UV-vis spectroscopy, [60] and confocal microscopy, [49] Auger electron spectroscopy, [71,72] and secondary ion mass spectrometry (SIMS). [73] …”

Section: X-ray Photoelectron Spectroscopy (Xps)mentioning

confidence: 99%

“…Gadzikwa et al [67] constructed a Zn-cornered, mixed-ligand, MOF bearing silane protected acetylene bonds that could be deprotected by using conventional organic chemistry. Such functionality would provide an extra level of control over the subsequent copper catalyzed azide alkyne coupling as Cu(I) catalyzes addition to terminal alkynes exclusively and it can be controlled where the cycloaddition occurs by selective deprotection.…”

Section: Miscellaneous Surfacesmentioning

confidence: 99%

Orthogonal Transformations on Solid Substrates: Efficient Avenues to Surface Modification

2009

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The performance of solid substrates is not only governed by their molecular constitution, but is also critically influenced by their surface constitution at the solid/gas or solid/liquid interface. In here, we critically review the use of orthogonal chemical transformations (so‐called click chemistry) to achieve efficient surface modifications of materials ranging from gold and silica nanoparticles, polymeric films, and microspheres to fullerenes as well as carbon nanotubes. In addition, the functionalization of surfaces via click chemistry with biomolecules is explored. Although a large host of reactions fulfilling the click‐criteria exist, pericyclic reactions are most frequently employed for efficient surface modifications. The advent of the click chemistry concept has led—as evident from the current literature—to a paradigm shift in current approaches for materials modification: Away from unspecific and nonselective reactions to highly specific true surface engineering.

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“…Typically PSM is applied using covalent interactions with the guest and the MOF's framework, however non-covalent interactions may be used as well [17]. When employing covalent interactions, there is large variety of organic reactions available; for example PSM has been applied for amide coupling [18], imine condensation [19,20], urea formation [21,22], bromination [23], N-alkylation [24], and click reactions [25,26]. Several of these PSM methods described have been demonstrated for MOF membranes/thin films in the literature.…”

Section: Introductionmentioning

confidence: 99%

Fabrication of a Substituted Imidazolate Material 1 (SIM-1) membrane using post synthetic modification (PSM) for pervaporation of water/ethanol mixtures

2015

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Post synthetic modification (PSM) of metal organic frameworks (MOFs) is a useful tactic used amongst researchers to refine a MOF's properties for an application of interest. In this report, we post synthetically modified a MOF known as Substituted Imidazolate Material 1 (SIM-1) to refine its molecular sieving potential. PSM of ethylenediamine, EDA, vapor was applied to a SIM-1 wafer. EDA cross-linked MOF crystals together through a Schiff base condensation reaction with SIM-1's reactive aldehyde linker forming a free-standing SIM-1 membrane. The membranes were tested for the separation of water from water/ethanol mixtures at room temperature. Results show that only water was detected by GC for all SIM-1 membrane permeates; this was consistent over the course of three separation cycles, whereas SIM-1 wafers without PSM fall apart after one separation cycle.

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Covalent surface modification of a metal–organic framework: selective surface engineering via CuI-catalyzed Huisgen cycloaddition

Abstract: A Zn-cornered, mixed-ligand, metal-organic framework (MOF) bearing TMS-protected acetylenes has been constructed and its surface decorated with organic molecules via'click chemistry', in a demonstration of selective post-synthesis functionalization.

Cited by 158 publications

References 23 publications

Postsynthetic Modification: A Versatile Approach Toward Multifunctional Metal-Organic Frameworks

Postsynthetic Modification: A Versatile Approach Toward Multifunctional Metal-Organic Frameworks

Orthogonal Transformations on Solid Substrates: Efficient Avenues to Surface Modification

Fabrication of a Substituted Imidazolate Material 1 (SIM-1) membrane using post synthetic modification (PSM) for pervaporation of water/ethanol mixtures

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