Intermolecular interactions in pi-stacked conjugated molecules. Synthesis,structure, and spectral characterization of alkyl bithiazole oligomers

Syntheses are reported of new 4,4'-dialkyl-2,2'-bithiazole oligomers that have alkenoxy side chains that are capable of easy conversion to oligomers with functionalized side chains, e.g., terminally substituted hydroxy chains. The crystal structures of two representative oligomers (4,4',4' ',4' "-tetra-(2-propenoxymethyl)-2,2',5',5' ',2' ',2' "-quaterthiazole (3P2) and 4,4',4' ',4' "-tetra-(3-hydroxypropyloxymethyl)-2,2',5',5' ',2' ',2' "-quaterthiazole (3H2)) were determined; 3P2 crystallizes in a pi-stacked motif with two molecules per unit cell, whereas 3H2 forms pi-stacks that are linked with hydrogen bonds to form infinite two-dimensional sheets with one molecule per unit cell. A comparison of the UV-vis spectra of the compounds in solution and in the solid state provides unequivocal evidence for the presence of a Davydov splitting, W(D) approximately 0.2 eV, in solid 3P2. The spectra are interpreted in the framework of molecular exciton theory to extract a value of the intermolecular transfer integral, J approximately 0.2 eV, for a total exciton bandwidth of ca. 0.8 eV. Monte Carlo calculations were used to determine the density of states of the exciton band and the absorption and emission line shapes of the 0 <-- 0 transition. It is suggested that the "three-humped" absorption profile typical of partially crystalline, regioregular polymers is the "optical signature" of pi-stacking.     

Lattice-Boltzmann simulations of the dynamics of polymer solutions in periodic and confined geometries

A numerical method to simulate the dynamics of polymer solutions in confined geometries has been implemented and tested. The method combines a fluctuating lattice-Boltzmann model of the solvent [Ladd, Phys. Rev. Lett. 70, 1339 (1993)] with a point-particle model of the polymer chains. A friction term couples the monomers to the fluid [Ahlrichs and Dunweg, J. Chem. Phys. 111, 8225 (1999)], providing both the hydrodynamic interactions between the monomers and the correlated random forces. The coupled equations for particles and fluid are solved on an inertial time scale, which proves to be surprisingly simple and efficient, avoiding the costly linear algebra associated with Brownian dynamics. Complex confined geometries can be represented by a straightforward mapping of the boundary surfaces onto a regular three-dimensional grid. The hydrodynamic interactions between monomers are shown to compare well with solutions of the Stokes equations down to distances of the order of the grid spacing. Numerical results are presented for the radius of gyration, end-to-end distance, and diffusion coefficient of an isolated polymer chain, ranging from 16 to 1024 monomers in length. The simulations are in excellent agreement with renormalization group calculations for an excluded volume chain. We show that hydrodynamic interactions in large polymers can be systematically coarse-grained to substantially reduce the computational cost of the simulation. Finally, we examine the effects of confinement and flow on the polymer distribution and diffusion constant in a narrow channel. Our results support the qualitative conclusions of recent Brownian dynamics simulations of confined polymers [Jendrejack et al., J. Chem. Phys. 119, 1165 (2003) and Jendrejack et al., J. Chem. Phys. 120, 2513 (2004)].     

Electron pair localization function: a practical tool to visualize electron localization in molecules from quantum Monte Carlo data

In this work we introduce an electron localization function describing the pairing of electrons in a molecular system. This function, called "electron pair localization function," is constructed to be particularly simple to evaluate within a quantum Monte Carlo framework. Two major advantages of this function are the following: (i) the simplicity and generality of its definition; and (ii) the possibility of calculating it with quantum Monte Carlo at various levels of accuracy (Hartree-Fock, multiconfigurational wave functions, valence bond, density functional theory, variational Monte Carlo with explicitly correlated trial wave functions, fixed-node diffusion Monte Carlo, etc). A number of applications of the electron pair localization function to simple atomic and molecular systems are presented and systematic comparisons with the more standard electron localization function of Becke and Edgecombe are done. Results illustrate that the electron pair localization function is a simple and practical tool for visualizing electronic localization in molecular systems.     

An anionic nucleophilic catalyst system for the diastereoselective synthesis of trans-beta-lactams

Trans-disubstituted beta-lactams show increasing utility and prominence in numerous pharmaceutical applications, making their asymmetric synthesis an attractive goal for chemists. We introduce an anionic, nucleophilic catalyst system that provides an efficient, diastereoselective route to trans-disubstituted beta-lactams, a complement to our previously described catalytic methodology for generating the corresponding cis diastereomers. This catalytic, "switch mechanism" process allows for flexibility in the stereoselective synthesis of beta-lactams, producing either cis or trans products as desired from the same substrates. [reaction: see text]     

An Unexpected Formation of a 14‐Membered Cyclodepsipeptide

The treatment of diluted solutions of the hydroxy diamides 6a and 6b in toluene with HCl gas at 100° gave the dimeric, 14‐membered cyclodepsipeptide 10 in up to 72% yield (Scheme 3). The same product was formed from the linear dimer of 6b , the depsipeptide 11 , under the same conditions (cf. Scheme 4). All attempts to prepare the cyclic seven‐membered monomer 9 , starting with different precursors and using different lactonization methods failed, and 10 was the only product which was isolated (cf. Scheme 6). For example, the reaction of the ester 20 with NaH in toluene at 80° led exclusively to the cyclodimer 10 . On the other hand, the base‐catalyzed cyclization of the hydroxy diester 22 , which is the ‘O‐analogue' of 20 , yielded neither the seven‐membered dilactone, nor the 14‐membered tetralactone, but only the known trimer 23 and tetramer 24 of 2,2‐dimethylpropano‐3‐lactone (cf. Scheme 7).     

Perchlorate analysis using solid-phase extraction cartridges

Perchlorate is a compound of increasing concern as an environmental contaminant and is being regulated at increasingly stringent levels. Reliable methods are needed to consistently analyze perchlorate at low concentration levels. This research investigates the use of solid-phase extraction cartridges as an alternative to large-volume injection loops to achieve low-level (microg/L level) perchlorate quantitation. The method involves commercially available strong anion exchange (SAX) cartridges. Water samples are filtered (100 to 1000 mL) using the cartridge, which removes the perchlorate from the solution by anion exchange. Then, after the desired volume is filtered, the perchlorate is extracted using 4 mL of 1% NaOH. In addition, a cleanup method is developed to remove competing anions (chloride, sulfate, and carbonate) that are often found in environmental samples. Analyses are performed with an ion chromatograph using a 10-microL injection loop, yielding a perchlorate method detection limit (MDL) of 210 microg/L. One-liter volumes of a 2-microg/L perchlorate spiked deionized water solution are filtered with SAX SPE. Following extraction and analysis, an MDL of 0.82 microg/L is obtained, comparable to that found for 1-mL injection loop systems (reported as low as 0.53 microg/L). MDL studies are then conducted on perchlorate-amended groundwater (solution concentration of 70 microg/L) and surface water (solution concentration of 10 microg/L) using a filtration volume of 200 mL. The MDLs are 6.7 microg/L for the groundwater and 2.4 microg/L for the surface water.     

Hydroxamic acid polymers

A polymer bearing hydroxamic acid groups and having a high affinity for iron(III) was prepared through the following procedure. Acryloylalanine (III), prepared by the reaction of acryloyl chloride with alanine, was treated with N-hydroxysuccinimide in the presence of dicyclohexylcarbodiimide to give the N-hydroxysuccinimide ester (IV). The ester IV was polymerized by using AIBN in dioxane to give polymer V. Treatment of polymer V with methylhydroxylamine in DMF gave the hydroxamic acid polymer II. The water-soluble polymer II was purified by dialysis or by gel-permeation chromatography (GPC) on Sephadex G-25. Analytical GPC on Sephadex G-200 and Sepharose 4B indicate that the average molecular weight of the polymer is in the range of 5 × 10⁵ to 1 × 10⁶. The presence of hydroxamic acid groups is confirmed by the intense red-brown color produced by the addition of iron(III) to a 50% aqueous DMF solution of the polymer under acidic conditions. In pure water the polymer-iron complex precipitates as a tan solid. Iron-binding studies of the polymer reveal that the iron(III) trihydroxamic acid complex FeA₃ forms at low concentrations of iron. At higher iron levels a lower order of stability is apparent, which can be accounted for by the conversion of FeA₃ to FeA₂⁺. In contrast, the FeA₃ complex of the trihydroxamic acid deferoxamine-B is stable at all iron levels. These results are consistent with the polymer structure, which for steric reasons would favor a stable complex, FeA₂⁺, between iron and two adjacent hydroxamic acid groups. An FeA₃ complex would be expected to have a lower stability as a result of either bond angle strain and atomic compression, or a lower probability in bringing a third hydroxamic acid into position to form the octahedral complex.     

Monodentate sigma-N and Bidentate sigma-N,sigma-N' Coordination of 1,1-Bis((N-p-tolylimino)diphenylphosphoranyl)ethane, CHCH(3)(PPh(2)=NC(6)H(4)-4-CH(3))(2), to Platinum(II)

The new ligand, 1,1-bis((N-p-tolylimino)diphenylphosphoranyl)ethane (1,1-BIPE), 1, has been synthesized by means of a Staudinger reaction of 1,1-bis(diphenylphosphino)ethane (1,1-dppe) with 2 equiv of p-tolylazide. Bridge-splitting reactions of Pt(2)Cl(4)(PR(3))(2) with 1 readily afforded sigma-N monodentate complexes, [PtCl(2)(PR(3)){1,1-BIPE-sigmaN}] (2a, PR(3) = PEt(3); 2b, PR(3) = PMe(2)Ph). Conversion of 2 into the six-membered platinacycle [PtCl(PR(3)){1,1-BIPE-sigmaN,sigmaN'}](+)[X](-) (3) (X = Cl, PtCl(3)(PR(3)), BF(4)) took place after prolonged stirring, its reaction rate being strongly dependent on the type of phosphine (>5 days for 2ain the presence of NaBF(4), 1 h for 2b) and the metal-to-ligand ratio. The compounds 1, 2, and 3 have been fully characterized by (1)H, (31)P{(1)H}, and (13)C{(1)H} NMR and IR spectroscopy, elemental analysis, or FAB mass spectroscopy. The molecular structures of CHCH(3)(PPh(2)=NC(6)H(4)-4-CH(3))(2) (1) and [PtCl(PMe(2)Ph){(N(pTol)=PPh(2))(2)CHCH(3)}](+)[Cl](-) (3b) have been determined by X-ray crystallography. Crystal data for 1: space group P2(1)/c with a = 8.9591(5) ?, b = 19.1961(12) ?, c = 21.9740(9) ?, beta = 105.069(4) degrees, V = 3649.1(3) ?(3), and Z = 4. The structure refinement converged to R = 0.080 and R(w) = 0.109. Crystal data for 3b: monoclinic, space group P2(1)/c with a = 12.4021(7) ?, b = 16.9705(11) ?, c = 23.760(2) ?, beta = 109.544(5) degrees, V = 4712.7(5) ?(3), and Z = 4. The structure refinement converged to R1 = 0.057, wR2 = 0.122. Variable temperature NMR spectroscopy has revealed that complexes 3 exclusively adopt a twisted boat conformation with the methyl group in equatorial position at low temperature, in agreement with the solid state structure of 3b as determined by X-ray crystallography. Boat-to-boat inversion is assumed to take place at temperatures above 293 K. Furthermore, for 3, hindered rotation of one of the p-tolyl substituents on nitrogen has been established at low temperatures.     

Synthesis of unsymmetrical 2,4-dialkylpyrazolo[1,5-a]-1,3,5-triazines

The reaction of 3-aminopyrazole with imidate esters such as ethyl acetimidate, gave N-(pyrazol-3-yl)acetamidine (1) rather than the isomeric 2-acetamidoyl-3-aminopyrazole. Ring closure of 1 with orthoesters such as ethyl propionimidate, afforded unsymmetrically substituted 2.4-dialkylpyrazolo[1,5-a]-1,3,5-triazines such as 4-ethyl-2-methylpyrazolo[1,5-a]-1,3,5-triazine (3). The structure of 1 was confirmed by several alternate syntheses. The unique feature of this two-step synthetic approach to the synthesis of pyrazolo[1,5-a]-1,3,5-triazines is that it is a convenient method of preparing fused triazines based on available pyrazoles rather than the less accessible dialkyltriazines.     

The solid solutions Na3(1−x)Alx2xPO4: room temperature powder neutron diffraction studies of the two compositions x=0.025 and x=0.2

The crystal structures of the high-temperature modifications of sodium and silver orthophosphates have been determined using powder neutron diffraction (PND) data. II-Na₃PO₄ adopts the space group Fm3m with at 400°C. The PO³⁻₄ group is centered around the origin, but it shows high orientational disorder. The sodium ions occupy the and sites. II-Ag₃PO₄, at 650°C, is similar with . The structure of I-Ag₃PO₄ at room temperature

Full-size image (<1K)

has been re-examined by single-crystal X-ray diffraction. The derived model, with R=0.019 for 116 independent reflections, is in agreement with the latest work reported in the literature. The structure of I-Ag₃PO₄ at 375°C, as determined by PND, has , and displays no gross modifications from that observed at 25°C, although the anisotropic nature of the silver sites is markedly more pronounced at this higher temperature. The cation mobility is discussed in relation to the high-temperatures structures.