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Self-assembled Structure of Inorganic-Organic Hybrid Crystals Based on Keggin Polyoxometallates [SMo12O402-] and Supramolecular Cations

To investigate the network structure of inorganic-organic hybrid crystals, we synthesized a series of assemblies based on polyoxometallates (POMs) [SMo12O402-] and different supramolecular cations consisting of anilinium and crown ether derivatives. The compounds [(m-XAni+)(B[18]crown-6)]2[SMo12O402-] (Ani+ = anilinium; B[18]crown-6 = benzo[18]crown-6; X = F (1), Cl (2), Br (3), or I (4)), [(4-MeAni+)(B[18]crown-6)]2[SMo12O402-]¡¤CH3CN (5), [(4-MeAni+)(DB[18]crown-6)]2[SMo12O402-]¡¤2CH3CN (6), [(3-F-4-MeAni+)(DB[18]crown-6)]2[SMo12O402-]¡¤2CH3CN (7), and [(3-F-4-MeAni+)2(DB[30]crown-10)][SMo12O402-]¡¤2CH3CN (8) (4-MeAni+ = 4-methylanilinium; DB[18]crown-6 = dibenzo[18]crown-6; 3-F-4-MeAni+ = 3-fluoro-4-methylanilinium; DB[30]crown-10 = dibenzo[30]crown-10) were synthesized. Their crystal architectures were characterized according to the size and charge of the supramolecular cations. In 1-4, two adjacent supramolecular cations ([(m-XAni+)(B[18]crown-6)]) were connected through pi?pi interactions forming sandwich-type dimers with the cations that were stacked in an antiparallel manner. In 8, DB[30]crown-10 included two cations constructing a larger divalent supramolecular cation [(3-F-4-MeAni+)2(DB[30]crown-10)]. In 1-4 and 8, the ratio between [SMo12O402-] and the supramolecular cations was 1:1, and the latter formed rectangular-assembled structures. In 5, the pi?pi stacking interaction was present in the adjacent B[18]crown-6. Monovalent supramolecular cations were present in 5-7 with a ratio of 1:2 between [SMo12O402-] and the supramolecular cations. The supramolecular cations formed hexagonal-assembled structures.

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Probing supramolecular complexation of cetylpyridinium chloride with crown ethers

Supramolecular complexations of cetylpyridinium chloride with three comparable cavity dimension based crown ethers, namely, dibenzo-18-crown-6, 18-crown-6 and dicyclohexano-18-crown-6 have been explored and adequately compared in acetonitrile with the help of conductivity in a series of temperatures to reveal the stoichiometry of the three host-guest complexes. Programme based mathematical treatment of the conductivity data affords association constants for complexations from which the thermodynamic parameters were derived for better comprehension about the process. The interactions at molecular level have been explained and decisively discussed by means of FT-IR and 1H NMR spectroscopic studies that demonstrate H-bond type interactions as the primarily force of attraction for the investigated supramolecular complexations.

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Influence of Polyethers on Properties of Aluminum Dust

A study was made of the dispersing and modifying action of perfluorinated oligopropylene oxide and dibenzo-18-crown-6 ether on aluminum powders being milled in a ball mill used for preparing highly reactive powders.

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Microhydration effects on the encapsulation of potassium ion by dibenzo-18-crown-6

We have measured electronic and conformer-specific vibrational spectra of hydrated dibenzo-18-crown-6 (DB18C6) complexes with potassium ion, K +?DB18C6?(H2O)n (n = 1-5), in a cold, 22-pole ion trap. We also present for comparison spectra of Rb +?DB18C6?(H2O)3 and Cs +?DB18C6?(H2O)3 complexes. We determine the number and the structure of conformers by analyzing the spectra with the aid of quantum chemical calculations. The K +?DB18C6?(H2O)1 complex has only one conformer under the conditions of our experiment. For K +?DB18C6?(H2O)n with n = 2 and 3, there are at least two conformers even under the cold conditions, whereas Rb+?DB18C6?(H2O)3 and Cs +?DB18C6?(H2O)3 each exhibit only one isomer. The difference can be explained by the optimum matching in size between the K+ ion and the crown cavity; because the K+ ion can be deeply encapsulated by DB18C6 and the interaction between the K+ ion and the H2O molecules becomes weak, different kinds of hydration geometries can occur for the K+?DB18C6 complex, giving multiple conformations in the experiment. For K+?DB18C6?(H 2O)n (n = 4 and 5) complexes, only a single isomer is found. This is attributed to a cooperative effect of the H2O molecules on the hydration of K+?DB18C6; the H2O molecules form a ring, which is bound on top of the K+?DB18C6 complex. According to the stable structure determined in this study, the K + ion in the K+?DB18C6?(H2O) n complexes tends to be pulled largely out from the crown cavity by the H2O molecules with increasing n. Multiple conformations observed for the K+ complexes will have an advantage for the effective capture of the K+ ion over the other alkali metal ions by DB18C6 because of entropic effects on the formation of hydrated complexes.

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Synthesis and complexing property of four-bridged crownopaddlanes

A new series of crown compounds crownopaddlanes 3a-c bearing three cyclobutane rings were prepared by means of intramolecular [2+2] photocycloaddition of styrene derivatives. The yield of crownopaddlane 3b possessing five ethereal oxygen atoms was remarkably high 52% with the addition of sodium borofluoride in the photoreaction system. As this template effect suggests, 3b showed extraordinarily high Na+-selectivity with high efficiency on the liquid-liquid extraction of alkali metal picrates, though 3a having four ethereal oxygen atoms did not extracted any cations in this system. The high Na+-selectivity of 3b was further clarified by the equilibrium stability constants (log Ka) for Na+ (5.85) and K+ (2.91) in acetonitrile solution. The complexation of 3b to Na+ cation was also examined by X-ray crystallography. Crownopaddlane 3c bearing six ethereal oxygen atoms also efficiently and selectively extracted alkali metal cations, compared with conventional 18-crown-6 derivatives.

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The Influence of Crown Ethers on Cation Migration Processes. Part 4. Some Simple Benzoquinone Radical Anions in the Presence of Dibenzo-18-crown-6

The radical anions of 2,5-di-t-butyl- and 2,5-dimethyl-benzoquinone have been prepared in 1,2-dimethoxyethane with Li+, Na+, or K+ as the counterion in the presence of dibenzo-18-crown-6.Linewidth alternation is observed in the e.s.r. spectra of these radical anions, with the lifetime of the counterion at one of the preferred sites near the radical anion varying in the sequence Li+ > Na+ > K+ at a particular temperature.It is apparent that in the presence of the crown ether ‘contact’ ion pairs are still present in the majority of the systems studied.The relatively minor influence of the crown ether on these systems is probably a result of the similarity in cation solvation environment presented by 1,2-dimethoxyethane and the crown ether.

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Reactivity of tris(allyl)aluminum toward pyridine: Coordination versus carbometalation

Tris(allyl)aluminum as its THF adduct, [Al(eta1-C 3H5)3(THF)] (1), reacted with pyridine either under substitution to give [Al(eta1-C3H 5)3(py)] (7) (py = pyridine) or under carbometalation to give N-metalated 2-allyldihydropyridine depending on the solvent. The substituent pattern of the pyridine substrate and the aluminum center’s electrophilicity in [Al(eta1-C3H5) 3(L)] (L = neutral ligand) influenced the outcome of the reaction. Reactions of one N-metalated dihydropyridine with electrophiles have been studied. A crystalline derivative of tris(allyl)aluminum, [Al(eta1- C3H5)3(OPPh3)] (2), and tetrakis(allyl)aluminate in the ion pair [K(15-crown-5)2] [Al(eta1-C3H5)4] (4) were characterized by single-crystal X-ray diffraction and shown to contain four-coordinate aluminum centers.

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The Structure of [HSi9]3? in the Solid State and Its Unexpected Highly Dynamic Behavior in Solution

We report on the first unambiguous detection of the elusive [HSi9]3? anion in solutions of liquid ammonia by various 29Si and 1H NMR experiments including chemical exchange saturation transfer (CEST). The characteristic multiplicity patterns of both the 29Si and 1H resonances together with CEST and a partially reduced 1H,29Si coupling constant indicate the presence of a highly dynamic Si8 entity and a Si?H moiety with slow proton hopping. Theoretical calculations corroborate both reorganization of Si8 on the picosecond timescale via low vibrational modes and proton hopping. In addition, in a single-crystal X-ray study of (K(DB[18]crown-6))(K([2.2.2]crypt))2[HSi9]?8.5 NH3, the H atom was unequivocally localized at one vertex of the basal square of the monocapped square-antiprismatic cluster. Thus experimental studies and theoretical considerations provide unprecedented insight into both the structure and the dynamic behavior of these cluster anions, which hitherto had been considered to be rigid.

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PREPARATION OF DIBENZO-18-CROWN-6 COMPLEXES OF CADMIUM(II) AND MERCURY(II), , AND MOLECULAR STRUCTURE OF

<(MX2(dbc)> complexes (M= Cd and Hg, X= Cl, Br, I, CN, and SCN) were prepared by heating an equimolar mixture of MX2 and dibenzo-18-crown-6 (dbc) in acetonitrile or toluene.A linear Cl-Hg-Cl moiety was found to be held perpendicularly in a quasi-planar ring of O6 from the X-ray crystal structure analysis.

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Synthesis and characterization of bis<1.1.1>orthocyclophano-18-crown-6 compounds

Two novel macrocyclic compounds 5S and 5A combining an 18-crown-6 and two cyclotriveratrylenes were synthesized by means of two methods from dibenzo-18-crown-6.The conformational isomers were separated using complexation with KSCN and their stereostructures were determined on the basis of 1H NMR spectroscopic and thermal equilibration studies.

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