Mesoporous Thin Films of “Molecular Squares” as Sensors for Volatile Organic Compounds

Keefe, Melinda H.; Slone, Robert V.; Hupp, Joseph T.; Czaplewski, Kenneth F.; Snurr, Randall Q.; Stern, Charlotte L.

doi:10.1021/la991252k

Cited by 90 publications

(76 citation statements)

References 55 publications

(49 reference statements)

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“…Comprising nearly all of this subset are molecular squares featuring cisligated Re(CO) 3 X (X ) Cl or Br) corners and rigid or semirigid difunctional azine or imine edges: compounds 2-9 shown. [28][29][30][31][32][33][34] They are typically obtained in a single step, in nearly quantitative yield, via a "coordinative self-assembly" process (Scheme 1). 31,35,36 The process makes use of Re(CO) 5 X as a simple synthon predisposed, via classical trans labilization effects, to liberate two (and only two) carbonyl ligands, exclusively from cis sites.…”

Section: Available Materialsmentioning

confidence: 99%

“…30,[80][81][82][83][84][85][86][87] Even fewer have focused on such behavior in the solid state. 28,31,35,38 A potentially significant advantage of a solid-state or materials approach over, for example, an approach based on a monolayer of receptor molecules, is the higher guest-uptake capacity available. Depending on the mode of signal transduction for successful uptake events, the higher capacity can translate into proportionately lower guest detection limits.…”

Section: Applications: Chemical Sensingmentioning

confidence: 99%

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Supramolecular Coordination Chemistry and Functional Microporous Molecular Materials

Dinolfo¹,

2001

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An enormous number and variety of discrete, isolable, supramolecular-coordinationchemistry-based assemblies featuring well-defined nanoscale cavities have been designed, synthesized, and characterized over the past decade. A small number of these have subsequently been used as building blocks for microporous materials and now comprise an important component of an emerging chemistry of microporous molecular materials. The extant materials typically have displayed large void volumes, high internal surface areas, and the ability to withstand the systematic removal of solvent. These and other properties (chemical tailorability, alignment of cavities to form extended channels, good processability, etc.) suggest a number of potentially very exciting applications involving selective molecular transport, sensing, or chemical transformationswith many of these now supported by proofof-concept experiments.

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Section: Available Materialsmentioning

confidence: 99%

Section: Applications: Chemical Sensingmentioning

confidence: 99%

Supramolecular Coordination Chemistry and Functional Microporous Molecular Materials

Dinolfo¹,

2001

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“…66, 67 The films exhibited a preference for aromatic guests (benzene) over aliphatic substrates (cyclohexane) and for good electron donors over poorer ones. This behavior did not depend on the metal used (Re or Mn).…”

Section: Sensingmentioning

confidence: 99%

Metallasupramolecular architectures, an overview of functional properties and applications

2006

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The synthesis of metallasupramolecular architectures, such as two-dimensional squares, triangles and polygons, and three-dimensional cages and polyhedra, has attracted much interest in the past decade. These structures are designed to have novel specific shapes and dimensions with interesting functional properties. In this overview the functional properties of metallasupramolecular architectures are highlighted with emphasis on potential applications such as catalysis, cavity-directed synthesis and sensing, that can be performed with these materials.

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“…The goals of this work are to demonstrate that molecular square membranes can also be used in vapor-phase applications and to gain insight into the selectivities that are observed. Results for permeation of single-component and binary mixtures of several volatile organic compounds (VOCs) are presented, and independent adsorption measurements [16,17] are then used to determine the role of sorption versus diffusion on permeability.…”

Section: Introductionmentioning

confidence: 99%

Vapor permeation studies of membranes made from molecular squares

Czaplewski¹,

Li²,

Hupp³

et al. 2003

Journal of Membrane Science

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Thin-film membranes have been made from cavity-containing supramolecular building blocks known as molecular squares and evaluated for simple test separations. Permeation properties of single components and binary gas mixtures were measured through membranes made of several different molecular squares. For a small square with pyrazine edges, permeation increased in the order cyclohexane < benzene < toluene, consistent with the selectivities predicted from the sorption coefficients. Diffusion rates also play an important role in the permeation selectivity. For a larger square with porphyrin edges, mixture selectivities for 4-picoline over toluene were observed to be around 7-9, depending on the partial pressure. Functionalization of the interior of the porpyrin square allowed a mixture selectivity of 7 for benzene over cyclohexane. Independently measured adsorption isotherms and effective diffusion coefficients proved very helpful in understanding the effects of sorption and diffusion on the observed permeabilities.

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Mesoporous Thin Films of “Molecular Squares” as Sensors for Volatile Organic Compounds

Cited by 90 publications

References 55 publications

Supramolecular Coordination Chemistry and Functional Microporous Molecular Materials

Supramolecular Coordination Chemistry and Functional Microporous Molecular Materials

Metallasupramolecular architectures, an overview of functional properties and applications

Vapor permeation studies of membranes made from molecular squares

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