Symmetry and the Role of the Anion Sublattice in Aurivillius Oxyfluoride BiTiOF.

The photocatalytic and dielectric behaviors of Aurivillius oxyfluorides such as BiTiOF depend sensitively on their crystal structure and symmetry but these are not fully understood. Our experimental work combined with symmetry analysis demonstrates the factors that influence anion order and how this might be tuned to break inversion symmetry. We explore an experimental approach to explore anion order, which combines Rietveld analysis with strain analysis.

The crystal engineering of radiation-sensitive diacetylene cocrystals and salts.

In this work we develop photoreactive cocrystals/salts of a commercially-important diacetylene, 10,12-pentacosadiynoic acid (PCDA, ) and report the first X-ray crystal structures of PCDA based systems. The topochemical reactivity of the system is modified depending on the coformer used and correlates with the structural parameters. Crystallisation of with 4,4'-azopyridine (), 4,4'-bipyridyl (), and -1,2-bis(4-pyridyl)ethylene () results in unreactive 2 : 1 cocrystals or a salt in the case of 4,4'-bipiperidine ().

Alkali Metal Salts of 10,12-Pentacosadiynoic Acid and Their Dosimetry Applications.

Wide-dose-range 2D radiochromic films for radiotherapy, such as GAFchromic EBT, are based on the lithium salt of 10,12-pentacosadiynoic acid (Li-PCDA) as the photosensitive component. We show that there are two solid forms of Li-PCDA-a monohydrated form A and an anhydrous form B. The form used in commercial GAFchromic films is form A due to its short needle-shaped crystals, which provide favorable coating properties.

Characterization of and Structural Insight into Struvite-K, MgKPO·6HO, an Analogue of Struvite.

Struvite-K (MgKPO·6HO) is a magnesium potassium phosphate mineral with naturally cementitious properties, which is finding increasing usage as an inorganic cement for niche applications including nuclear waste management and rapid road repair. Struvite-K is also of interest in sustainable phosphate recovery from wastewater and, as such, a detailed knowledge of the crystal chemistry and high-temperature behavior is required to support further laboratory investigations and industrial applications. In this study, the local chemical environments of synthetic struvite-K were investigated using high-field solid-state Mg and K MAS NMR techniques, alongside P MAS NMR and thermal analysis.

Tweaking the Charge Transfer: Bonding Analysis of Bismuth(III) Complexes with a Flexidentate Phosphane Ligand.

To account for the charge transfer and covalent character in bonding between P and Bi centers, the electronic structures of [P(CH--CHSCH)BiCl] ( = 0-3) model species have been investigated computationally. On the basis of this survey a synthetic target compound with a dative P→Bi bond has been selected. Consecutively, the highly reactive bismuth cage [P(CH--CHSCH)Bi] has been accessed experimentally and characterized.

A One-Pot Divergent Sequence to Pyrazole and Quinoline Derivatives.

The hydroxy-pyrazole and 3-hydroxy-oxindole motifs have been utilised in several pharma and agrochemical leads but are distinctly underrepresented in the scientific literature due to the limited routes of preparation. We have developed a one-pot procedure for their synthesis starting from simple isatins. The method employs cheap and easy-to-handle building blocks and allows easy isolation.

Framework Effects on Activation and Functionalisation of Methane in Zinc-Exchanged Zeolites.

The first selective oxidation of methane to methanol is reported herein for zinc-exchanged MOR (Zn/MOR). Under identical conditions, Zn/FER and Zn/ZSM-5 both form zinc formate and methanol. Selective methane activation to form [Zn-CH ] species was confirmed by C MAS NMR spectroscopy for all three frameworks.

Enhancing the Efficiency of a Dye-Sensitized Solar Cell Based on a Metal Oxide Nanocomposite Gel Polymer Electrolyte.

To overcome the critical limitations of liquid-electrolyte-based dye-sensitized solar cells, quasi-solid-state electrolytes have been explored as a means of addressing long-term device stability, albeit with comparatively low ionic conductivities and device performances. Although metal oxide additives have been shown to augment ionic conductivity, their propensity to aggregate into large crystalline particles upon high-heat annealing hinders their full potential in quasi-solid-state electrolytes. In this work, sonochemical processing has been successfully applied to generate fine CoO nanoparticles that are highly dispersible in a PAN:P(VP--VAc) polymer-blended gel electrolyte, even after calcination.

Weak Pnictogen Bond with Bismuth: Experimental Evidence Based on Bi-P Through-Space Coupling.

To study pnictogen bonding involving bismuth, flexible accordion-like molecular complexes of the composition [P(C H -o-CH SCH ) BiX ], (X=Cl, Br, I) have been synthesised and characterised. The strength of the weak and mainly electrostatic interaction between the Bi and P centres strongly depends on the character of the halogen substituent on bismuth, which is confirmed by single-crystal X-ray diffraction analyses, DFT and ab initio computations. Significantly, Bi- P through-space coupling (J=2560 Hz) is observed in solid-state P NMR spectra, which is so far unprecedented in the literature, delivering direct information on the magnitude of this pnictogen interaction.

Solid state C NMR spectroscopy provides direct evidence for reaction between ethinyl estradiol and a silicone elastomer vaginal ring drug delivery system.

Steroid molecules have a long history of incorporation into silicone elastomer materials for controlled release drug delivery applications. Previously, based on in vitro release testing and drug content analysis, we demonstrated indirectly that the contraceptive progestin levonorgestrel (LNG) chemically and irreversibly binds to addition cure silicone elastomers, presumably via a hydrosilylation reaction between the levonorgestrel ethynyl group and the hydrosilane groups in the poly(dimethylsiloxane-co-methylhydrosiloxane) crosslinker of the silicone elastomer. Here, for the first time, we report that solid state C nuclear magnetic resonance (NMR) spectroscopy provides direct evidence for the irreversible binding of ethinyl estradiol (EE) - an estrogenic steroid molecule also containing an ethynyl functional group - to an addition cure silicone elastomer.

Tin and Lead Phosphanido Complexes: Reactivity with Chalcogens.

The reactivity of tin and lead phosphanido complexes with chalogens is reported. The addition of sulfur to [(BDI)MPCy] (M = Sn, Pb; BDI = CH{(CH)CN-2,6-iPrCH}) results in the formation of phosphinodithioates [(BDI)MSP(S)Cy] regardless of the conditions; however, when selenium is added to [(BDI)MPCy], a selenium insertion product, phosphinoselenoite [(BDI)MSePCy], can be isolated. This compound readily reacts with additional selenium to form the phosphinodiselenoate complex [(BDI)MSeP(Se)Cy].

Characterization of Two Distinct Amorphous Forms of Valsartan by Solid-State NMR.

Valsartan (VAL) is an antihypertensive drug marketed in an amorphous form. Amorphous materials can have different physicochemical properties depending on preparation method, thermal history, etc., but the nature of such materials is difficult to study by diffraction techniques.

Na(+) mobility in sodium strontium silicate fast ion conductors.

We present the first direct evidence of Na-ion mobility in sodium strontium silicate fast ion conductors, based on variable temperature (23)Na solid state NMR spectroscopy and spin-lattice relaxation measurements.

Synthesis, Structure, and Reactivity of Anionic sp(2) -sp(3) Diboron Compounds: Readily Accessible Boryl Nucleophiles.

Lewis base adducts of tetra-alkoxy diboron compounds, in particular bis(pinacolato)diboron (B2 pin2 ), have been proposed as the active source of nucleophilic boryl species in metal-free borylation reactions. We report the isolation and detailed structural characterization (by solid-state and solution NMR spectroscopy and X-ray crystallography) of a series of anionic adducts of B2 pin2 with hard Lewis bases, such as alkoxides and fluoride. The study was extended to alternative Lewis bases, such as acetate, and other diboron reagents.

Complex thermal expansion properties in a molecular honeycomb lattice.

[FeL3][BF4]2·xH2O (L = 3-(pyrazinyl)-1H-pyrazole) shows negative thermal expansion between 150-240 K but positive thermal expansion at 240-300 K, linked to rearrangement of anions and water molecules within pores in the lattice.

New solvates of an old drug compound (phenobarbital): structure and stability.

The solvent formation of phenobarbital, an important drug compound with an unusually complex polymorphic behavior, was studied in detail. Monosolvates with acetonitrile, nitromethane, dichloromethane, and 1,4-dioxane were produced and characterized by single-crystal and powder X-ray diffraction, thermoanalytical methods, FT-IR, Raman, and solid-state NMR spectroscopy. Thermal desolvation of these compounds yields mainly mixtures of polymorphs III, II, and I.

Crystal polymorphs of barbital: news about a classic polymorphic system.

Barbital is a hypnotic agent that has been intensely studied for many decades. The aim of this work was to establish a clear and comprehensible picture of its polymorphic system. Four of the six known solid forms of barbital (denoted I(0), III, IV, and V) were characterized by various analytical techniques, and the thermodynamic relationships between the polymorph phases were established.

NMR characterisation of dynamics in solvates and desolvates of formoterol fumarate.

Solid-state NMR is used to characterise dynamics in the ethanol solvate of the pharmaceutical material formoterol fumarate and its associated desolvate. Jump rates and activation barriers for dynamic processes such as phenyl ring rotation and methyl group rotational diffusion are derived from 1D-EXSY and (13)C spin-lattice relaxation times respectively. (2)H and (13)C spin-lattice relaxation times measured under magic-angle spinning conditions are used to show that the fumarate ion in the desolvate is undergoing small-amplitude motion on a frequency scale of 100s of MHz at ambient temperature with an activation parameter of about 32 kJ mol(-1).

Structure of cellulose microfibrils in primary cell walls from collenchyma.

In the primary walls of growing plant cells, the glucose polymer cellulose is assembled into long microfibrils a few nanometers in diameter. The rigidity and orientation of these microfibrils control cell expansion; therefore, cellulose synthesis is a key factor in the growth and morphogenesis of plants. Celery (Apium graveolens) collenchyma is a useful model system for the study of primary wall microfibril structure because its microfibrils are oriented with unusual uniformity, facilitating spectroscopic and diffraction experiments.

NMR characterisation of structure in solvates and polymorphs of formoterol fumarate.

The solid-state structures of two polymorphs and two alcoholates (ethanol and isopropanol) of formoterol fumarate have been investigated by a combination of NMR techniques. First-principles shielding computations are combined with NMR data to successfully relate peaks to their crystallographic positions for the solvates, including atoms that are in equivalent molecular positions. The uncharacterised structure of the asolvate form C is found to contain a single formoterol ion and half a fumarate ion in its asymmetric unit.

Synthesis and characterization of a rhodium(I) σ-alkane complex in the solid state.

Transition metal-alkane complexes-termed σ-complexes because the alkane donates electron density to the metal from a σ-symmetry carbon-hydrogen (C-H) orbital-are key intermediates in catalytic C-H activation processes, yet these complexes remain tantalizingly elusive to characterization in the solid state by single-crystal x-ray diffraction techniques. Here, we report an approach to the synthesis and characterization of transition metal-alkane complexes in the solid state by a simple gas-solid reaction to produce an alkane σ-complex directly. This strategy enables the structural determination, by x-ray diffraction, of an alkane (norbornane) σ-bound to a d(8)-rhodium(I) metal center, in which the chelating alkane ligand is coordinated to the pseudosquare planar metal center through two σ-C-H bonds.

Group 14 metal terminal phosphides: correlating structure with |J(MP)|.

A series of heavier group 14 element, terminal phosphide complexes, M(BDI)(PR(2)) (M = Ge, Sn, Pb; BDI = CH{(CH(3))CN-2,6-iPr(2)C(6)H(3)}(2); R = Ph, Cy, SiMe(3)) have been synthesized. Two different conformations (endo and exo) are observed in the solid-state; the complexes with an endo conformation have a planar coordination geometry at phosphorus (M = Ge, Sn; R = SiMe(3)) whereas the complexes possessing an exo conformation have a pyramidal geometry at phosphorus. Solution-state NMR studies reveal through-space scalar coupling between the tin and the isopropyl groups on the N-aryl moiety of the BDI ligand, with endo and exo exhibiting different J(SnC) values.

Spectroscopic and structural characterization of the CyNHC adduct of B2pin2 in solution and in the solid state.

The Lewis base adduct of B(2)pin(2) and the NHC (1,3-bis(cyclohexyl)imidazol-2-ylidene), which was proposed to act as a source of nucleophilic boryl groups in the β-borylation of α,β-unsaturated ketones, has been isolated, and its solid state structure and solution behavior was studied. In solution, the binding is weak, and NMR spectroscopy reveals a rapid exchange of the NHC between the two boron centers. DFT calculations reveal that the exchange involves dissociation and reassociation of NHC rather than an intramolecular process.

Nanostructure of cellulose microfibrils in spruce wood.

The structure of cellulose microfibrils in wood is not known in detail, despite the abundance of cellulose in woody biomass and its importance for biology, energy, and engineering. The structure of the microfibrils of spruce wood cellulose was investigated using a range of spectroscopic methods coupled to small-angle neutron and wide-angle X-ray scattering. The scattering data were consistent with 24-chain microfibrils and favored a "rectangular" model with both hydrophobic and hydrophilic surfaces exposed.

Zinc(II) silsesquioxane complexes and their application for the ring-opening polymerization of rac-lactide.

In this Communication, we report the unprecedented solid-state structures for a series of zinc(II) silsesquioxane complexes. Initial catalytic data for the ring-opening polymerization of rac-lactide are also presented together with analogous heterogeneous species.