Electrosynthesis of a Biaurone by Controlled Dimerization of Flavone: Mechanistic Insight and Large-Scale Application.

The electrochemistry of flavone (1) has been carefully investigated at glassy carbon cathodes in dimethylformamide containing 0.10 M tetra-n-butylammonium tetrafluoroborate as supporting electrolyte. In this medium, a cyclic voltammogram for a reduction of 1 exhibits a reversible cathodic process (Epc = -1.58 V and Epa = -1.47 V vs SHE) that is followed by an irreversible cathodic peak (Epc = -2.17 V vs SHE). When water (5.0 M) is introduced into the medium, the first peak for 1 becomes irreversible (Epc = -1.56 V vs SHE), and the second (irreversible) peak shifts to -2.07 V vs SHE. Bulk electrolyses of 1 at -1.60 V vs SHE afford flavanone, 2'-hydroxychalcone, 2'-hydroxy-3-phenylpropionate, and two new compounds, namely (Z)-1,6-bis(2-hydroxyphenyl)-3,4-diphenylhex-3-ene-1,6-dione (D1) and (Z)-2,2'-(1,2-diphenylethene-1,2-bis(benzofuran-3(2H))-one) (D2), obtained in significant amounts, that were characterized by means of 1H and 13C NMR spectrometry as well as single-crystal X-ray diffraction. Along with the above findings, we have proposed a mechanism for the electroreduction of 1, which has been further corroborated by our quantum mechanical study.

Phosphate-phosphate oligomerization drives higher order co-assemblies with stacks of cyanostar macrocycles.

The importance of phosphate in biology and chemistry has long motivated investigation of its recognition. Despite this interest, phosphate's facile oligomerization is only now being examined following the discovery of complexes of anion-anion dimers of hydroxyanions. Here we address how oligomerization dictates phosphate's recognition properties when engaged with planar cyanostar macrocycles that can also oligomerize by stacking. The crystal structure of cyanostar with phosphate shows an unprecedented tetrameric stack of cyanostar macrocycles threaded by a phosphate trimer, [H2PO4···H2PO4···H2PO4]3-. The solution behaviour, studied as a function of solvent quality, highlights how dimers and trimers of phosphate drive formation of higher order stacks of cyanostar into dimer, trimer and tetramer co-assemblies. Solution behaviors differ significantly from simpler complexes of bisulfate hydroxyanion dimers. Phosphate oligomerization is: (1) preferred over ion pairing with tetrabutylammonium cations, (2) inhibits disassembly of the complexes upon dilution, and (3) resists interference from competitive anion solvation. The phosphate oligomers also appear critical for stability; complexation of just one phosphate with cyanostars is unfavored. The cyanostar's ability to self-assemble is found to create a tubular, highly electropositive cavity that complements the size and shape of the phosphate oligomers as well as their higher charge. When given the opportunity, phosphate will cooperate with the receptor to form co-assembled architectures.

Ion Pairing and Co-facial Stacking Drive High-Fidelity Bisulfate Assembly with Cyanostar Macrocyclic Hosts.

Hydroxyanions pair up inside CH H-bonding cyanostar macrocycles against Coulombic repulsions and solvation forces acting to separate them. The driving forces responsible for assembly of bisulfate (HSO4- ) dimers are unclear. We investigated them using solvent quality to tune the contributing forces and we take advantage of characteristic NMR signatures to follow the species distributions. We show that apolar solvents enhance ion pairing to stabilize formation of a 2:2:2 complex composed of π-stacked cyanostars encapsulating the [HSO4 ⋅⋅⋅HSO4 ]2- dimer and endcapped by tetrabutylammonium cations. Without cations engaged, a third macrocycle can be recruited with the aid of solvophobic forces in more polar solvents. The third macrocycle generates a more potent electropositive pocket in which to stabilize the anti-electrostatic anion dimer as a 3:2 assembly. We also see unprecedented evidence for a water molecule bound to the complex in the acetonitrile solution. In methanol, OH H-bonding leads to formation of 2:1 complexes by bisulfate solvation inside the macrocycles inhibiting anion dimers. Knowledge of the driving forces for stabilization (strong OH⋅⋅⋅O H-bonding, CH H-bonding, ion pairs, π-stacking) competing with destabilization (Coulomb repulsion, solvation) allows high-fidelity selection of the assemblies. Thermodynamic stabilization of hydroxyanion dimers also demonstrates the ability to use macrocycles to control ion speciation and stoichiometry of the overall assemblies.

19 F DOSY diffusion-NMR spectroscopy of fluoropolymers.

A new pulse sequence for obtaining 19 F detected DOSY (diffusion ordered spectroscopy) spectra of fluorinated molecules is presented and used to study fluoropolymers based on vinylidene fluoride and chlorotrifluoroethylene. The performance of 19 F DOSY NMR experiments (and in general any type of NMR experiment) on fluoropolymers creates some unique complications that very often prevent detection of important signals. Factors that create these complications include: (1) the presence of many scalar couplings among 1 H, 19 F and 13 C; (2) the large magnitudes of many 19 F homonuclear couplings (especially 2 JFF ); (3) the large 19 F chemical shift range; and (4) the low solubility of these materials (which requires that experiments be performed at high temperatures). A systematic study of the various methods for collecting DOSY NMR data, and the adaptation of these methods to obtain 19 F detected DOSY data, has been performed using a mixture of low molecular weight, fluorinated model compounds. The best pulse sequences and optimal experimental conditions have been determined for obtaining 19 F DOSY spectra. The optimum pulse sequences for acquiring 19 F DOSY NMR data have been determined for various circumstances taking into account the spectral dispersion, number and magnitude of couplings present, and experimental temperature. Pulse sequences and experimental parameters for optimizing these experiments for the study of fluoropolymers have been studied. Copyright © 2016 John Wiley & Sons, Ltd.

Anions Stabilize Each Other inside Macrocyclic Hosts.

Contrary to the simple expectations from Coulomb's law, Weinhold proposed that anions can stabilize each other as metastable dimers, yet experimental evidence for these species and their mutual stabilization is missing. We show that two bisulfate anions can form such dimers, which stabilize each other with self-complementary hydrogen bonds, by encapsulation inside a pair of cyanostar macrocycles. The resulting 2:2 complex of the bisulfate homodimer persists across all states of matter, including in solution. The bisulfate dimer's OH⋅⋅⋅O hydrogen bonding is seen in a 1 H NMR peak at 13.75 ppm, which is consistent with borderline-strong hydrogen bonds.

Quantifying chloride binding and salt extraction with poly(methyl methacrylate) copolymers bearing aryl-triazoles as anion receptor side chains.

Copolymers of methyl methacrylate and aryl-triazole based anion receptors were quantitatively analyzed. Transfer of structural features (1 : 1 and 2 : 1 complexes) and Cl(-) affinities from the parent receptors was demonstrated. Cl(-)-induced cross-linking changed the polymer's hydrodynamic radius. Extraction of tetrapropylammonium Cl(-) from water to dichloromethane was enhanced over PMMA.

Structure and conformation of the medium-sized chlorophosphazene rings.

Medium-sized cyclic oligomeric phosphazenes [PCl2N]m (where m = 5-9) that were prepared from the reaction of PCl5 and NH4Cl in refluxing chlorobenzene have been isolated by a combination of sublimation/extraction and column chromatography from the predominant products [PCl2N]3 and [PCl2N]4. The medium-sized rings [PCl2N]m have been characterized by electrospray ionization-mass spectroscopy (ESI-MS), their (31)P chemical shifts have been reassigned, and their T1 relaxation times have been obtained. Crystallographic data has been recollected for [PCl2N]5, and the crystal structures of [PCl2N]6, and [PCl2N]8 are reported. Halogen-bonding interactions were observed in all the crystal structures of cyclic [PCl2N]m (m = 3-5, 6, 8). The crystal structures of [P(OPh)2N]7 and [P(OPh)2N]8, which are derivatives of the respective [PCl2N]m, are also reported. Comparisons of the intermolecular forces and torsion angles of [PCl2N]8 and [P(OPh)2N]8 with those of three other octameric rings are described. The comparisons show that chlorophosphazenes should not be considered prototypical, in terms of solid-state structure, because of the strong influence of halogen bonding.

Rotational energy barrier of 2-(2',6'-dihydroxyphenyl)benzoxazole: a case study by NMR.

2-(2'-Hydroxyphenyl)benzoxazole (HBO) derivatives represent an important class of luminescent materials, as they can undergo excited state intramolecular proton transfer (ESIPT). The material's ESIPT properties are dependent on the ratio of two different rotamers, whose interconversion is poorly understood. By using HBO derivative 4, the rotational energy barrier of 2- (2',6'-hydroxyphenyl)benzoxazole is determined to be 10.5 kcal/mol by variable-temperature NMR. Although a HBO derivative typically exhibits two rotamers with O···H-O (e.g., 1a) and N···H-O bonding (e.g., 1b), correlation of NMR with fluorescence data reveals that the rotamer with N···H-O bonding is predominant in the solution.