Contact Stabilization of Host Molecules during Clathrate Formation

Dyadin, Yuri A.; Kislykh, N. V.

doi:10.1070/mc1991v001n04abeh000083

Cited by 29 publications

(6 citation statements)

References 2 publications

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“…As illustrated here, this impact can be enough to switch the mode of bond formation, thus re-directing the entire compound formation process. Recently similar observations were reported for some Werner clathrates where van der Waals forces were found to stabilize not only conformations but also molecular isomers and molecules …”

Section: Resultssupporting

confidence: 81%

Inclusion in Microporous β-Bis(1,1,1-trifluoro-5,5-dimethyl-5- methoxyacetylacetonato)copper(II), an Organic Zeolite Mimic

Soldatov

Ripmeester

2000

Chem. Mater.

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In this contribution, we show that the porous β-form of the title complex preserves its host lattice pore structure in the presence of more than 100 guests. Among the species that are able to promote the α-to-β transformation and that are capable of being included as guests are the gaseous and condensed hydrocarbons, their halo derivatives, alcohols, diols, aldehydes, ketones, ethers, esters, ethers of inorganic acids, acids, nitriles, and a variety of substituted aromatics. The empty β-form behaves like a microporous sponge, instantly absorbing significant quantities even of highly volatile compounds such as methane, ethane, and propane. The material demonstrates zeolite-like behavior, not only from the robustness of the empty pore structure, but also from its propensity for efficient adsorption and desorption. The thermal stability of inclusions with normal paraffins increases from 142 °C (incongruent melting) to 163.5 °C (true melting) in the series from n-C5 to n-C16, while the guest-free α-form of the complex melts at 157 °C. The interaction of the complex with alcohols illustrates competing options between chemical bonding to copper and physical sorption into the microporous β-form. Methanol and ethanol coordinate to copper, thereby taking part in building, respectively, 2-D and 1-D polymers, whereas higher alcohols induce conversion to a 3-D β-form, stabilizing this porous modification by inclusion. From the observed stoichiometry and thermal stability, the host matrix is shown to be capable of molecular recognition of alcohols that have a shape and dimensions complementary to available pore geometry. Finally, the prospects for the rational design of new 3-D microporous polymers of bis-chelate building blocks are discussed.

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Section: Resultssupporting

confidence: 81%

Inclusion in Microporous β-Bis(1,1,1-trifluoro-5,5-dimethyl-5- methoxyacetylacetonato)copper(II), an Organic Zeolite Mimic

Soldatov

Ripmeester

2000

Chem. Mater.

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“…The most important factor for the higher stability of the α form seems to be its higher packing efficiency of 56.5% as compared to 50.6% for the β polymorph (Table ). Packing efficiency is a very important factor for molecular crystals, and that was recently demonstrated for other organic and metal-organic supramolecular systems. − …”

Section: Resultsmentioning

confidence: 96%

The First “Organic Zeolite” with Isomerizing Building Blocks: Single-Crystal-to-Single-Crystal Desolvation and Structure of the Empty Matrix

Soldatov

Grachev

Ripmeester

2002

Crystal Growth & Design

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The microporous β polymorph of the title compound has been prepared as a crystalline product by slow removal of the guest from the inclusion compound with methylene chloride, [CuL 2 ]*2/3(CH 2 Cl 2 ) (L is 1,1,1trifluoro-5,5-dimethyl-5-methoxyacetylacetonate, {CF 3 COCHCOC(CH 3 ) 2 OCH 3 } -). Collapse of the crystals of the β polymorph into the thermodynamically stable R form has been studied by visual observation and DSC calorimetry, the product exhibiting much higher kinetic stability than the polycrystalline samples prepared so far. The crystal structure of the β polymorph was determined by single-crystal XRD methods both at 293 and 173 K. The β polymorph retains the same 3D polymeric coordination framework as found previously in inclusion compounds of the complex. The structures of the β and R polymorphs are compared and the variation of the β matrix in a series of compounds was analyzed. The β framework described in this work seems to be the most flexible of all coordination polymers known so far, preserving its microporous structure upon guest exchange or removal; the complete range of change in molar volume observed for the matrix is 8.6%.

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“…Guest-induced change of the molecular structure of host complexes is an attractive but still not well explored way to switch bulk properties of supramolecular materials. 17 Guest-supported stabilization in supramolecular solids of molecular conformations, ,,− spatial isomers, ,− and the molecules themselves − was traced in the literature, but there seemed to be very few examples of guest-supported stabilization of an oligomeric host complex. , …”

Section: Resultsmentioning

confidence: 99%

Modified Metal Dibenzoylmethanates for Soft Supramolecular Materials: Extension to Oligomeric and Polymeric Host Receptors with Nanosized Void Spaces

et al. 2003

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Recently reported molecular host complexes, modified metal dibenzoylmethanates (metal DBMs), are extended to polynuclear host receptors by connecting metal DBM units with bridging ligand 4,4′-dipyridyl (bipy). Series of new solvent-free as well as inclusion materials were prepared and studied with XRD, NMR, and other methods. Template-directed synthesis gave inclusion compounds with three distinct types of host receptors: dimeric [Zn 2 (bipy)-(DBM) 4 ], trimeric [Zn 3 (bipy) 2 (DBM) 6 ], and polymeric [Zn(bipy)(DBM) 2 ] n complexes. The dimeric complex was isolated as a solvent-free compound and as inclusion compounds with tert-butylbenzene and fluorobenzene (host per guest molar ratios of 1:1 and 1: 2 / 3 , respectively). The trimeric complex was prepared as an inclusion compound with DMSO (1:5 molar ratio). The polymeric complex was observed in inclusion compounds with fluorobenzene (host unit per guest molar ratio 1:2), tetrahydrofuran (1:2), 2-pentanone (1:2), bipy/DMSO (1: 1 / 2 : 1 / 2 ), and bipy/tert-butylbenzene (1:1:2); a solvent-free material was obtained upon desolvation of tetrahydrofuran and 2-pentanone inclusions. The isolated host species have five-coordinated terminal zinc centers (two chelating DBMs and a singly coordinating bipy) and octahedrally coordinated intrinsic zinc centers (two chelating equatorial DBMs and two singly coordinating bipys). The bipy ligands bridge the zinc centers to give the di-, tri-, and polynuclear complexes. Nanosized voids between the DBM units coordinated to adjacent zinc centers form the basis for cages and channels in the inclusion materials. These voids have, in many cases, a typical size of between 1 and 2 nm and accommodate up to five molecules per single cavity or two rows of guest molecules in a single channel. When compared to previously reported metal DBMs, the multinuclear metal DBM receptors reported here exhibit stronger inclusion affinity and enhanced inclusion capacity.

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Contact Stabilization of Host Molecules during Clathrate Formation

Cited by 29 publications

References 2 publications

Inclusion in Microporous β-Bis(1,1,1-trifluoro-5,5-dimethyl-5- methoxyacetylacetonato)copper(II), an Organic Zeolite Mimic

Inclusion in Microporous β-Bis(1,1,1-trifluoro-5,5-dimethyl-5- methoxyacetylacetonato)copper(II), an Organic Zeolite Mimic

The First “Organic Zeolite” with Isomerizing Building Blocks: Single-Crystal-to-Single-Crystal Desolvation and Structure of the Empty Matrix

Modified Metal Dibenzoylmethanates for Soft Supramolecular Materials: Extension to Oligomeric and Polymeric Host Receptors with Nanosized Void Spaces

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