Fluoride‐Ion Encapsulation within a Silsesquioxane Cage

Bassindale, Alan R.; Pourny, Manuel; Taylor, Peter G.; Hursthouse, Michael B.; Light, Mark E.

doi:10.1002/ange.200351249

Cited by 31 publications

(20 citation statements)

References 22 publications

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“…Hydroxyl groups can serve as selective sites for metal complexation and cation addition to enhance hydrogen adsorption. [37] In addition, as the D4R cages can trap very small species such as atomic hydrogen and fluoride ion, [38] post-synthetic incorporation of fluoride ions into the PSNs would lead to anionic porous polymeric hybrids.…”

Section: Resultsmentioning

confidence: 99%

Hybrid Porous Materials with High Surface Area Derived from Bromophenylethenyl‐Functionalized Cubic Siloxane‐Based Building Units

Chaikittisilp

Sugawara

Shimojima

et al. 2010

Chemistry A European J

117

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Sonogashira cross-coupling of bromophenylethenyl-terminated cubic, double four-ring, siloxane cages with di-/triethynyl compounds results in microporous poly(ethynylene aryleneethenylene silsesquioxane) networks, simply termed as polyorganosiloxane networks (PSNs). In comparison with porous organic polymers reported previously, these PSNs show relatively high surface area and comparable thermal stability. Their apparent BET specific surface areas vary in the range of 850-1040 m(2) g(-1) depending on the length and the connectable sites of the ethynyl compounds. Analyses of pore size distribution revealed bimodal micropores with relatively narrow distribution. The degree of cross-linking affects the degree of cleavage of the siloxane bonds, and this suggests that partial cleavage of the siloxane cages is mainly a result of cage distortion. Hydrogen adsorption was performed to evaluate potential of the PSNs as hydrogen storage media. Uptakes of up to 1.19 wt% at 77 K and 760 Torr and initial isosteric heats of adsorption as high as 8.0 kJ mol(-1) were observed. These materials have been obtained by a combination of structural, synthetic organic, and materials chemistry, which can exploited to synthesize porous hybrid materials with specifically designed structures and functions.

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Section: Resultsmentioning

confidence: 99%

Hybrid Porous Materials with High Surface Area Derived from Bromophenylethenyl‐Functionalized Cubic Siloxane‐Based Building Units

Chaikittisilp

Sugawara

Shimojima

et al. 2010

Chemistry A European J

117

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“…Another important aspect of POSS chemistry is its interaction with fluorine source. Previously, Bassindale and co‐workers discovered the encapsulation of a fluorine atom within the POSS core (Figure ) . This interesting chemical event was studied in greater depth by the same group .…”

Section: Poss Chemistrymentioning

confidence: 89%

Cubic Polyhedral Oligomeric Silsesquioxane Based Functional Materials: Synthesis, Assembly, and Applications

Zhou

2016

Chemistry An Asian Journal

152

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Organically modified cubic polyhedral oligomeric silsesquioxanes (POSS) have attracted increasing attention in the design of novel functional hybrid materials for applications such as porous materials, liquid crystals, semiconductors, high-temperature lubricants, fuel cells, and lithium batteries. The nanosized POSS moiety can be conveniently modified on the periphery with a variety of functional groups to lead to hybrid materials with desired functions. In addition, suitable mono-functionalized POSS derivatives can be incorporated into polymers as side chains via various synthetic strategies to offer a wide class of functional polymeric materials with tunable physical properties for targeted applications. In this Focus Review, we aim to summarize the recent developments on the chemistry and applications of POSS-based molecules and polymers. Moreover, the properties as well as assembly behavior of the POSS-based functional hybrid materials will be reviewed, and the relationship of the performance of the hybrid materials with the intrinsic nature of the POSS unit will be addressed.

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“…Ac ouple of ingenious species are known for encapsulating fluoride,o racovalent XÀFl inkage in ac age, [4] as sometimes in olden days aforementioned wild cats were put in cages for good or ill. Forinstance,Bassindale and co-workers have synthesized an inclusion compound in which al one fluoride ion resides in as iloxane cage (1,F igure 1). [4a] Additionally,P ascal and co-workers have ensconced as ilyl fluoride linkage in ac age that forces it into close proximity with the p-system of an arene (2,F igure 1).…”

Section: Introductionmentioning

confidence: 99%

Fluorine in a C−F Bond as the Key to Cage Formation

2018

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Cage molecules have long been employed to trap reactive or transient species, as their rigid nature allows them to enforce situations that otherwise would not persist. In this Minireview, we discuss our use of rigid cage structures to investigate the close noncovalent interactions of fluorine with other functional groups and determine how mutual proximity affects both physical properties and reactivity. Unusual covalent interactions of fluorine are also explored: the cage can close to form the first solution-phase C-F-C fluoronium ion.

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Fluoride‐Ion Encapsulation within a Silsesquioxane Cage

Cited by 31 publications

References 22 publications

Hybrid Porous Materials with High Surface Area Derived from Bromophenylethenyl‐Functionalized Cubic Siloxane‐Based Building Units

Hybrid Porous Materials with High Surface Area Derived from Bromophenylethenyl‐Functionalized Cubic Siloxane‐Based Building Units

Cubic Polyhedral Oligomeric Silsesquioxane Based Functional Materials: Synthesis, Assembly, and Applications

Fluorine in a C−F Bond as the Key to Cage Formation

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