High‐Loading Crystals of Tetraaryladamantanes and the Uptake and Release of Aromatic Hydrocarbons from the Gas Phase

Alexandre, P.; Schwenger, Alexander; Frey, Wolfgang; Richert, Clemens

doi:10.1002/chem.201701060

Cited by 22 publications

(45 citation statements)

References 13 publications

(26 reference statements)

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“…Stable crystalline inclusion complexes with reagents as different in structure and polarity as acetyl chloride, piperidine, cyclohexyl isocyanide and trimethylsilyl chloride were obtained (Schwenger et al 2016). The ethyl derivative 1,3,5,7-tetrakis(2,4-diethoxyphenyl)adamantane (TEO) was then found to accommodate up to 3.5 equivalents of guest molecules in its crystals and to capture and release liquid aromatic hydrocarbons via the gas phase (Alexandre et al 2017). Recently, cyclopentadiene was shown to be stabilized against dimerization by inclusion in TDA crystals, extending the scope of the crystal-based "formulations" to self-reactive organic substrates (Krupp et al 2018).…”

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confidence: 99%

Non-porous organic crystals and their interaction with guest molecules from the gas phase

et al. 2020

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Some organic molecules encapsulate solvents upon crystallization. One class of compounds that shows a high propensity to form such crystalline solvates are tetraaryladamantanes (TAAs). Recently, tetrakis(dialkoxyphenyl)-adamantanes have been shown to encapsulate a wide range of guest molecules in their crystals, and to stabilize the guest molecules against undesired reactions. The term ‘encapsulating organic crystals’ (EnOCs) has been coined for these species. In this work, we studied the behavior of three TAAs upon exposition to different guest molecules by means of sorption technique. We firstly measured the vapor adsorption/desorption isotherms with water, tetrahydrofuran and toluene, and secondly, we studied the uptake of methane on dry and wet TAAs. Uptake of methane beyond one molar equivalent was detected for wet crystals, even though the materials showed a lack of porosity. Thus far, such behavior, which we ascribe to methane hydrate formation, had been described for porous non-crystalline materials or crystals with detectable porosity, not for non-porous organic crystals. Our results show that TAA crystals have interesting properties beyond the formation of conventional solvates. Gas-containing organic crystals may find application as reservoirs for gases that are difficult to encapsulate or are slow to form crystalline hydrates in the absence of a host compound. Wet tetraaryladamantane crystals take up methane in form of methane hydrate structure I, even though they appear non-porous to argon.

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confidence: 99%

Non-porous organic crystals and their interaction with guest molecules from the gas phase

et al. 2020

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“…Tetraaryladamantanes are known to form crystalline inclusion complexes for a wide range of small molecules, 6,7,8,9 and the resulting solids have been referred to as 'encapsulating organic crystals' (EnOCs). 10 Thermal cocrystallization is rapid, does not require screening for suitable solvents, and produced well diffracting co-crystals for the majority of over 50 liquid compounds tested.…”

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Determining the Relative Configuration of Propargyl Cyclopropanes by Co-Crystallization

Krupp

Picher

Frey

et al. 2020

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Determining the diastereoselectivity of new synthetic molecules can be a challenge when NMR methods fail and the compounds are difficult to crystallize. Encapsulating organic crystals (EnOCs) can be used to overcome this challenge. Here we show that the diastereomeric configuration of racemic mixtures of propargyl cyclopropanes can be determined by co-crystallization with 1,3,5,7-tetrakis(2-bromo-4-methoxyphenyl)adamantane (TBro) and X-ray crystallography. Three crystal structures are reported that unambiguously identify the products of Fe-catalyzed cyclopropanations as cis- or trans-isomers. These findings expand the scope of co-crystallization with tetraaryladamantanes as a method to determine the stereochemical configuration of organic molecules that are difficult to crystallize by themselves.

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“… Structures and representative crystal forms of tetraaryladamantane EnOCs, as described in the recent literature 12 14 …”

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“…Some reagent formulations of water-sensitive compounds are stable to air, or, as in the case of benzoyl chloride encapsulated in TEO, stable to immersion in water. 14 …”

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Encapsulating Organic Crystals (EnOCs)

Richert

Krupp

2017

Synlett

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Achieving efficient capture, storage and release of small molecules is a challenge. Most materials that can harbor small molecules have been studied in the context of gas storage or separation. Formulations for hazardous reagents have only recently attracted attention, when organic compounds were discovered that encapsulate a broad range of guest molecules in crystals. Such encapsulating organic crystals (EnOCs) can suppress problematic properties of reagents and allow for controlled release in reaction mixtures. Unlike materials used for gas storage, which possess permanent porosity, their cavities are not held together by covalent or strong noncovalent interactions. Instead, EnOCs crystallize with the help of weaker packing forces. Substituted tetraaryladamantane octaethers can form high-loading inclusion compounds with reagents as guests, but they can also transition into tightly packed, solvate-free forms. Here we highlight the differences between EnOCs and known porous materials and discuss the potential of EnOCs as formulations in organic synthesis.

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High‐Loading Crystals of Tetraaryladamantanes and the Uptake and Release of Aromatic Hydrocarbons from the Gas Phase

Cited by 22 publications

References 13 publications

Non-porous organic crystals and their interaction with guest molecules from the gas phase

Non-porous organic crystals and their interaction with guest molecules from the gas phase

Determining the Relative Configuration of Propargyl Cyclopropanes by Co-Crystallization

Encapsulating Organic Crystals (EnOCs)

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