Single-Crystal-to-Single-Crystal Postsynthetic Modification of a Metal–Organic Framework via Ozonolysis

Albalad, Jorge; Xu, Heng; Gándara, Felipe; Haouas, Mohamed; Martineau‐Corcos, Charlotte; Mas‐Ballesté, Rubén; Barnett, Sarah A.; Juanhuix, Jordi; Imaz, Inhar; Maspoch, Daniel

doi:10.1021/jacs.7b12913

Cited by 56 publications

(59 citation statements)

References 31 publications

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“…Note that the peak intensity of protons from the olefinic bond at 7.70 ppm (orange dot) was very weak but it could still be observed, indicating a high degree of cleavage but not quantitative. Moreover, the signal of the proton at 6.64 ppm (red star) was identified as the intermediate trioxolane-metathesis product, which is in accordance with the previous paper published by our group (6) S6.…”

Section: Fig S11 (A)supporting

confidence: 90%

Clip-off Chemistry: Synthesis by Programmed Disassembly of Reticular Materials

Yang¹,

Broto‐Ribas²,

Ortín‐Rubio³

et al. 2021

Preprint

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<p><a>Bond-breaking is an essential process in natural and synthetic chemical transformations. Accordingly, the ability for researchers to strategically dictate which bonds in a given system are broken translates to greater synthetic control, as historically evidenced in fields such as organic synthesis. Here, we report extending the concept of selective bond-breaking to reticular materials, in a new synthetic approach that we call Clip-off Chemistry. We show that bond-breaking in these structures can be controlled at the molecular level; is periodic, quantitative and selective; is effective in reactions performed in either solid or liquid phases</a>; and can occur in a single-crystal-to-single crystal fashion involving the entire bulk precursor sample. Clip-off Chemistry opens the door to programmed disassembly of reticular materials and thus, to the design and synthesis of new molecules and materials.</p><p><br></p><br><div><br></div>

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Section: Fig S11 (A)supporting

confidence: 90%

Clip-off Chemistry: Synthesis by Programmed Disassembly of Reticular Materials

Yang¹,

Broto‐Ribas²,

Ortín‐Rubio³

et al. 2021

Preprint

Self Cite

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“…[ 69 ] An interesting work depicts a solvent‐less solid–gas approach, where ozone gas was used to convert the olefins into the 1,2,4‐trioxalane rings quantitatively and the rings were further reduced to aldehydes and ketones or oxidized to carboxylic acids. [ 70 ]…”

Section: Psm In Mofsmentioning

confidence: 99%

Post‐Synthetic Modification of Metal–Organic Frameworks Toward Applications

Mandal

Natarajan

Mani

et al. 2020

Adv Funct Materials

337

207

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Post‐synthetic modification (PSM) of metal–organic framework (MOF) compounds is a useful technique for preparing new MOFs that can exhibit or enhance many of the properties of the parent MOFs. PSM can be carried out by a number of approaches such as modifying the linker (ligand) and/or metal node, and adsorption/exchange of guest species. The surface environment of the MOF can be modified to increase structural stability as well as introducing desired properties. There is considerable scope in widening the applications of the MOF with compatible metal or ligand employing the PSM. This review focuses on the recent developments of modified materials through PSM, which augers well for the chemical modification and functionalization of MOFs. In this review, different types of PSM methods are presented in an orderly manner, and the diverse applications of resultant frameworks are described and discussed.

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“…The alkene groups in MUF‐88‐v are reactive and thus amenable to postsynthetic modification reactions. Related reports have shown that halogenation, thiol‐ene and ozonolysis reactions are possible on related materials. We reacted MUF‐88‐v with Br 2 in dichloromethane at room temperature to obtain MUF‐88‐Br (Figure ).…”

Section: Resultsmentioning

confidence: 98%

Thermal Elimination of Ethylene from Cyclobutyl Groups Characterized by X‐ray Crystallography in a Metal–Organic Framework Matrix

Alkaş

Friche

Harris

et al. 2020

Chemistry A European J

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Methods to synthesize and characterize aromatic molecules with vinyl substituents are sought after yet limited in the literature. Here, we introduce cyclobutyl groups into a metal–organic framework (MOF) matrix that are poised to produce ethylene upon heating. The expulsion of ethylene produces vinyl groups on an aromatic core, which are isolated by the crystalline matrix of the framework. This enables full characterization of the thermolysis by single‐crystal X‐ray diffraction. Further, we modify the vinyl groups by a bromine addition reaction. Importantly, the two transformations happen in a single‐crystal‐to‐single‐crystal manner without changing the overall network structure of the parent framework. New insights into the structural and synthetic chemistry of this important class of compound are generated. Installing reactive vinyl tags in materials by the high temperature thermolysis of cyclobutyl groups is a powerful strategy for altering their physicochemical characteristics.

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Single-Crystal-to-Single-Crystal Postsynthetic Modification of a Metal–Organic Framework via Ozonolysis

Cited by 56 publications

References 31 publications

Clip-off Chemistry: Synthesis by Programmed Disassembly of Reticular Materials

Clip-off Chemistry: Synthesis by Programmed Disassembly of Reticular Materials

Post‐Synthetic Modification of Metal–Organic Frameworks Toward Applications

Thermal Elimination of Ethylene from Cyclobutyl Groups Characterized by X‐ray Crystallography in a Metal–Organic Framework Matrix

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