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The photocatalytic and dielectric behaviors of Aurivillius oxyfluorides such as Bi 2 TiO 4 F 2 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.

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. Form B provides an enhanced photoresponse compared to that of form A, but adopts a long needle crystal morphology, which is difficult to process. The two forms were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, CP-MAS 13 C solid-state NMR spectroscopy, and thermogravimetric analysis. In sum, these data suggest a chelating bridging bidentate coordination mode for the lithium ions. The sodium salt of PCDA (Na-PCDA) is also reported, which is an ionic cocrystal with a formula of Na + PCDA - ·3PCDA. The PCDA and PCDA - ligands display monodentate and bridging bidentate coordination to the sodium ion in contrast to the coordination sphere of the Li-PCDA forms. In contrast to its lithium analogues, Na-PCDA is photostable., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

Struvite-K (MgKPO 4 ·6H 2 O) 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 25 Mg and 39 K MAS NMR techniques, alongside 31 P MAS NMR and thermal analysis. A single resonance was present in each of the 25 Mg and 39 K MAS NMR spectra, reported here for the first time alongside the experimental and calculated isotropic chemical shifts, which were comparable to the available data for isostructural struvite (MgNH 4 PO 4 ·6H 2 O). An in situ high-temperature XRD analysis of struvite-K revealed the presence of a crystalline-amorphous-crystalline transition that occurred between 30 and 350 °C, following the single dehydration step of struvite-K. Between 50 and 300 °C, struvite-K dehydration yielded a transient disordered (amorphous) phase identified here for the first time, denoted δ-MgKPO 4 . At 350 °C, recrystallization was observed, yielding β-MgKPO 4 , commensurate with an endothermic DTA event. A subsequent phase transition to γ-MgKPO 4 was observed on further heating, which reversed on cooling, resulting in the α-MgKPO 4 structure stabilized at room temperature. This behavior was dissimilar from that of struvite exposed to high temperature, where NH 4 liberation occurs at temperatures >50 °C, indicating that struvite-K could potentially withstand high temperatures via a transition to MgKPO 4 .

In this work we develop photoreactive cocrystals/salts of a commercially-important diacetylene, 10,12-pentacosadiynoic acid (PCDA, 1 ) 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 1 with 4,4'-azopyridine ( 2 ), 4,4'-bipyridyl ( 3 ), and trans -1,2-bis(4-pyridyl)ethylene ( 4 ) results in unreactive 2 : 1 cocrystals or a salt in the case of 4,4'-bipiperidine ( 5 ). However, salt formation with morpholine ( 6 ), diethylamine ( 7 ), and n -butylamine ( 8 ), results in highly photoreactive salts 12·7 and 1·8 whose reactivity can be explained using topochemical criteria. The salt 1·6 is also highly photoreactive and is compared to a model morpholinium butanoate salt. Resonance Raman spectroscopy reveals structural details of the photopolymer including its conformational disorder in comparison to less photoactive alkali metal salts and the extent of solid state conversion can be monitored by CP-MAS NMR spectroscopy. We also report an unusual catalysis in which amine evaporation from photopolymerised PCDA ammonium salts effectively acts as a catalyst for polymerisation of PCDA itself. The new photoreactive salts exhibit more reactivity but decreased conjugation compared to the commercial lithium salt and are of considerable practical potential in terms of tunable colours and greater range in UV, X-ray, and γ-ray dosimetry applications., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

To account for the charge transfer and covalent character in bonding between P and Bi centers, the electronic structures of [P(C 6 H 4 - o -CH 2 SCH 3 ) 3 BiCl n ] (3- n )+ ( n = 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(C 6 H 4 - o -CH 2 SCH 3 ) 3 Bi] 3+ has been accessed experimentally and characterized. Importantly, our experiments (single-crystal X-ray diffraction and solid-state NMR spectroscopy) and computations (NBO and AIM analysis) reveal that the P···Bi bonding in this trication can be described as a dative bond. Here we have shown that our accordion-like molecular framework allows for tuning of the interaction between P and Bi centers.

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.

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 3 ] + species was confirmed by 13 C MAS NMR spectroscopy for all three frameworks. The percentage of active zinc sites, measured through quantitative NMR spectroscopy studies, varied with the zeolite framework and was found to be ZSM-5 (5.7 %), MOR (1.2 %) and FER (0.5 %). For Zn/MOR, two signals were observed in the 13 C MAS NMR spectrum, resulting from two distinct [Zn-CH 3 ] + species present in the 12 MR and 8 MR side pockets, as supported by additional NMR experiments. The observed products of oxidation of the [Zn-CH 3 ] + species are shown to depend on the zeolite framework type and the oxidative conditions used. These results lay the foundation for developing structure-function correlations for methane conversion over zinc-exchanged zeolites., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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 Co 3 O 4 nanoparticles that are highly dispersible in a PAN:P(VP- co -VAc) polymer-blended gel electrolyte, even after calcination. An optimized nanocomposite gel polymer electrolyte containing 3 wt % sonicated Co 3 O 4 nanoparticles (PVVA-3) delivers the highest ionic conductivity (4.62 × 10 -3 S cm -1 ) of the series. This property is accompanied by a 51% enhancement in the apparent diffusion coefficient of triiodide versus both unmodified and unsonicated electrolyte samples. The dye-sensitized solar cell based on PVVA-3 displays a power conversion efficiency of 6.46% under AM1.5 G, 100 mW cm -2 . By identifying the optimal loading of sonochemically processed nanoparticles, we are able to generate a homogenous extended particle network that effectively mobilizes redox-active species through a highly amorphous host matrix. This effect is manifested in a selective 51% enhancement in photocurrent density ( J SC = 16.2 mA cm -2 ) and a lowered barrier to N719 dye regeneration ( R CT = 193 Ω) versus an unmodified solar cell. To the best of our knowledge, this work represents the highest known efficiency to date for dye-sensitized solar cells based on a sonicated Co 3 O 4 -modified gel polymer electrolyte. Sonochemical processing, when applied in this manner, has the potential to make meaningful contributions toward the ongoing mission to achieve the widespread exploitation of stable and low-cost dye-sensitized solar cells.

To study pnictogen bonding involving bismuth, flexible accordion-like molecular complexes of the composition [P(C 6 H 4 -o-CH 2 SCH 3 ) 3 BiX 3 ], (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, 209 Bi- 31 P through-space coupling (J=2560 Hz) is observed in solid-state 31 P NMR spectra, which is so far unprecedented in the literature, delivering direct information on the magnitude of this pnictogen interaction., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

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 13 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. By preparing silicone elastomer samples containing 13 C-labelled EE, signals in the NMR spectra could readily be assigned to both the free and bound EE. Additional depolymerisation studies, performed on an addition cure silicone elastomer system from which the unbound EE fraction was completely extracted, further confirmed the presence of bound EE through the formation of coloured reaction mixtures resulting from the reaction of bound EE and trifluoroacetic acid (TFA). These methods will be particularly useful in the ongoing development of new steroid-releasing silicone drug delivery devices, including various vaginal ring devices for contraception, HIV prevention and multipurpose prevention technology applications., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Sequential treatment of a previously-calcined solid oxide support (i.e. SiO 2 , γ-Al 2 O 3 , or mixed SiO 2 -Al 2 O 3 ) with solutions of Cr{N(SiMe 3 ) 2 } 3 (0.71 wt% Cr) and a Lewis acidic alkyl aluminium-based co-catalyst (15 molar equivalents) affords initiator systems active for the oligomerisation and/or polymerisation of ethylene. The influence of the oxide support, calcination temperature, co-catalyst, and reaction diluent on both the productivity and selectivity of the immobilised chromium initiator systems have been investigated, with the best performing combination (SiO 2-600 , modified methyl aluminoxane-12 {MMAO-12}, heptane) producing a mixture of hexenes (61 wt%; 79% 1-hexene), and polyethylene (16 wt%) with an activity of 2403 g g Cr -1  h -1 . The observed product distribution is rationalised by two competing processes: trimerisation via a supported metallacycle-based mechanism and polymerisation through a classical Cossee-Arlman chain-growth pathway. This is supported by the indirect observation of two distinct chromium environments at the surface of the oxide support by a solid-state 29 Si NMR spectroscopic study of the Cr{N(SiMe 3 ) 2 } x /SiO 2-600 pro-initiator.

The reactivity of tin and lead phosphanido complexes with chalogens is reported. The addition of sulfur to [(BDI)MPCy 2 ] (M = Sn, Pb; BDI = CH{(CH 3 )CN-2,6-iPr 2 C 6 H 3 } 2 ) results in the formation of phosphinodithioates [(BDI)MSP(S)Cy 2 ] regardless of the conditions; however, when selenium is added to [(BDI)MPCy 2 ], a selenium insertion product, phosphinoselenoite [(BDI)MSePCy 2 ], can be isolated. This compound readily reacts with additional selenium to form the phosphinodiselenoate complex [(BDI)MSeP(Se)Cy 2 ]. In contrast, the addition of selenium to [(BDI)SnP(SiMe 3 ) 2 ] results in the formation of the heavy ether [(BDI)SnSeSiMe 3 ]. Differences in the solution and solid-state molecular species of tin phosphinoselenoite and phosphinodiselenoate complexes were probed using multinuclear solution and solid-state NMR spectroscopy.

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. This study characterizes two different amorphous forms of valsartan (AR and AM) using solid-state NMR (SSNMR) as a primary investigation tool, supported by solution-state NMR, FT-IR, TMDSC, and dissolution tests. The two forms are found to be clearly distinct, with a significantly higher level of structural arrangement in the AR form, as observed in (13)C, (15)N, and (1)H SSNMR. (13)C and (15)N NMR indicates that the fully amorphous material (AM) contains an approximately equal ratio of cis-trans conformers about the amide bond, whereas the AR form exists mainly as one conformer, with minor conformational "defects". (1)H ultrafast MAS NMR shows significant differences in the hydrogen bonding involving the tetrazole and acid hydrogens between the two materials, while (15)N NMR shows that both forms exist as a 1,2,3,4-tetrazole tautomer. NMR relaxation times show subtle differences in local and bulk molecular mobility, which can be connected with the glass transition, the stability of the glassy material, and its response to aging. Counterintuitively the fully amorphous material is found to have a significantly lower dissolution rate than the apparently more ordered AR material.

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.

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. The B(sp(2) )-B(sp(3) ) adducts exhibit two distinct boron environments in the solid-state and solution NMR spectra, except for [(4-tBuC6 H4 O)B2 pin2 ](-) , which shows rapid site exchange in solution. DFT calculations were performed to analyze the stability of the adducts with respect to dissociation. Stoichiometric reaction of the isolated adducts with two representative series of organic electrophiles-namely, aryl halides and diazonium salts-demonstrate the relative reactivities of the anionic diboron compounds as nucleophilic boryl anion sources., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

[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.

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. At a low relative humidity (25 °C) the solvates transform to polymorph III, and at higher relative humidity the monohydrate and the metastable polymorphs IV and VI can be present as additional desolvation products. These results highlight the potential complexity of desolvation reactions and illustrate that a tight control of ambient conditions is a prerequisite for the production of phase-pure raw materials of drug compounds. Transformation in aqueous media results in the monohydrate. Below room temperature, the 1,4-dioxane monosolvate undergoes a reversible single-crystal-to-single-crystal phase transition due to the ordering/disordering of 50% of its solvent molecules. Dipolar-dephasing NMR experiments show that the solvent molecules are relatively mobile. Deuterium NMR spectra reinforce that conclusion for the dioxane solvent molecules. The crystal structure of an elusive 1,4-dioxane hemisolvate was also determined. This study clearly indicates the existence of "transient solvates" of phenobarbital. The formation of unstable phases of this kind must be considered in order to better understand how different solvents affect the crystallization of specific polymorphs.

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. The obtained data permitted the construction of the first semischematic energy/temperature diagram for the barbital system. The modifications I(0), III, and V are enantiotropically related to one another. Polymorph IV is enantiotropically related to V and monotropically related to the other two forms. The transition points for the pairs I(0)/III, I(0)/V, and III/IV lie below 20 °C, and the transition point for IV/V is above 20 °C. At room temperature, the order of thermodynamic stability is I(0) > III > V > IV. The metastable modification III is present in commercial samples and has a high kinetic stability. The solid-state NMR spectra provide information on aspects of crystallography (viz., the asymmetric units and the nature of hydrogen bonding). The known correlation between specific N-H···O═C hydrogen bonding motifs of barbiturates and certain IR characteristics was used to predict the H-bonded pattern of polymorph IV.

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). Exact calculations of relaxation times under MAS provide a simple and robust means to test motional models in cases where relaxation rate maxima are observed, including for systems where the crystal structure of the material is unknown.

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. Using a combination of x-ray and neutron scattering methods with vibrational and nuclear magnetic resonance spectroscopy, we show that celery collenchyma microfibrils were 2.9 to 3.0 nm in mean diameter, with a most probable structure containing 24 chains in cross section, arranged in eight hydrogen-bonded sheets of three chains, with extensive disorder in lateral packing, conformation, and hydrogen bonding. A similar 18-chain structure, and 24-chain structures of different shape, fitted the data less well. Conformational disorder was largely restricted to the surface chains, but disorder in chain packing was not. That is, in position and orientation, the surface chains conformed to the disordered lattice constituting the core of each microfibril. There was evidence that adjacent microfibrils were noncovalently aggregated together over part of their length, suggesting that the need to disrupt these aggregates might be a constraining factor in growth and in the hydrolysis of cellulose for biofuel production.

In this paper we examine the effect of Ga doping on the structure and conductivity of the high Li ion content garnet-related system, La(3)Zr(2)Li(7)O(12). Without Ga doping, La(3)Zr(2)Li(7)O(12) is tetragonal and has low Li ion conductivity. The introduction of Ga leads to a change to a cubic unit cell, and a large enhancement in the conductivity. Prior structural studies of La(3)Zr(2)Li(7)O(12) have shown the presence of both tetrahedral and distorted octahedral sites for Li, and the low conductivity can be explained by the ordered nature of the Li distribution. The present structural study of La(3)Zr(2)Ga(0.5)Li(5.5)O(12) shows that Ga substitutes onto the tetrahedral site. Despite the presence of non-mobile Ga(3+) on the Li sites, the conductivity is enhanced as a result of the introduction of vacancies in the Li sites, and consequent disorder on the Li sublattice. Further work has suggested that over time in air, there is some H(+)/Li(+) exchange, and consequently some variation in the conductivity.

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. HETCOR experiments for the ethanolate and form C allow proton chemical shifts to be determined and give improved (13)C resolution for the former compound. Desolvation of the solvates to form C has been monitored under the conditions of the NMR experiment. Differential rates of phenylene ring flipping are observed in the different forms. Carbon-13 relaxation times and (2)H NMR are used to probe dynamics of the fumarate ion., (Copyright © 2012 John Wiley & Sons, Ltd.)

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.

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. The magnitudes of the tin-phosphorus and lead-phosphorus coupling constants, |J(SnP)| and |J(PbP)|, differ significantly depending upon the hybridization of the phosphorus atom. For Sn(BDI)(P{SiMe(3)}(2)), |J(SnP)| is the largest reported in the literature, surpassing values attributed to compounds with tin-phosphorus multiple-bonds. Low temperature NMR studies of Pb(BDI)(P{SiMe(3)}(2)) show two species with vastly different |J(PbP)| values, interpreted as belonging to the endo and exo conformations, with sp(2)- and sp(3)-hybridized phosphorus, respectively.

In this paper we report the successful synthesis of the cubic oxyanion containing perovskites, Ba(2)Sc(2-x)P(x)O(5+x) (x = 0.4, 0.5), with the samples analysed through a combination of X-ray diffraction, NMR, TGA, Raman spectroscopy and conductivity measurements. Conductivity measurements indicate a p-type contribution to the conductivity in oxidizing conditions at elevated temperatures, with evidence for proton conduction in wet atmospheres. For the latter, bulk conductivities of 5.9 × 10(-3) and 1.3 × 10(-3) S cm(-1) at 500 °C were obtained for x = 0.4 and 0.5 respectively, comparable to other perovskite proton conductors, while the stability towards CO(2) containing atmospheres was improved compared to BaCeO(3) based systems. Related Si doped systems have also been prepared, although in this case small Ba(2)SiO(4) impurities are observed. We also provide evidence to suggest that "undoped" Ba(2)Sc(2)O(5) contains carbonate groups, which accounts for its thermal instability.

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.

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. Disorder in chain packing and hydrogen bonding was shown to increase outwards from the microfibril center. The extent of disorder blurred the distinction between the I alpha and I beta allomorphs. Chains at the surface were distinct in conformation, with high levels of conformational disorder at C-6, less intramolecular hydrogen bonding and more outward-directed hydrogen bonding. Axial disorder could be explained in terms of twisting of the microfibrils, with implications for their biosynthesis.

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.

Powder X-ray diffraction (XRD) has been exploited to establish the structural properties of a porous interpenetrated mixed-ligand metal-organic framework material prepared by solid-state grinding, recognizing that product phases from mechanochemical synthesis are typically microcrystalline powders. The importance of subjecting the powder XRD data to rigorous scrutiny in such applications is emphasized.

A range of chloroindate(iii) ionic liquid systems was prepared by mixing of 1-alkyl-3-methylimidazolium chloride with indium(iii) chloride in various ratios, expressed as the mol fraction of indium(iii) chloride, chi(InCl(3)). For chi(InCl(3)) 0.50, the products were biphasic (suspensions of a solid in an ionic liquid). Speciation of these chloroindate(iii) systems was carried out using a wide range of techniques: differential scanning calorimetry (DSC), polarised optical microscopy (POM), liquid-state and solid-state (115)In NMR spectroscopy, X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS). Ionic liquids prepared using an excess of the organic chloride (chi(InCl(3)) < 0.5) contained [InCl(6)](3-), [InCl(5)](2-) and [InCl(4)](-) anions, in proportions dependent on the chi(InCl(3)) value. Equimolar mixtures yielded single compounds: 1-alkyl-3-methylimidazolium tetrachloroindates(iii). Systems containing an excess of indium(iii) chloride (chi(InCl(3)) > 0.5) contained indium(iii) chloride powder suspended in a neutral tetrachloroindate ionic liquid.

The bis-guanidino compound H(2)C{hpp}(2) (I; hppH = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) has been converted to the monocation [I-H](+) and isolated as the chloride and tetraphenylborate salts. Solution-state spectroscopic data do not differentiate the protonated guanidinium from the neutral guanidino group but suggest intramolecular "-N-H...N=" hydrogen bonding to form an eight-membered C(3)N(4)H heterocycle. Solid-state CPMAS (15)N NMR spectroscopy confirms protonation at one of the imine nitrogens, although line broadening is consistent with solid-state proton transfer between guanidine functionalities. X-ray diffraction data have been recorded over the temperature range 50-273 K. Examination of the carbon-nitrogen bond lengths suggests a degree of "partial protonation" of the neutral guanidino group at higher temperatures, with greater localization of the proton at one nitrogen position as the temperature is lowered. Difference electron density maps generated from high-resolution X-ray diffraction studies at 110 K give the first direct experimental evidence for proton transfer in a poly(guanidino) system. Computational analysis of I and its conjugate acid [I-H](+) indicate strong cationic resonance stabilization of the guanidinium group, with the nonprotonated group also stabilized, albeit to a lesser extent. The maximum barrier to proton transfer calculated using the Boese-Martin for kinetics method was 2.8 kcal mol(-1), with hydrogen-bond compression evident in the transition state; addition of zero-point vibrational energy values leads to the conclusion that the proton transfer is barrierless, implying that the proton shuttles freely between the two nitrogen atoms. Calculations determining the gas-phase proton affinity and the pK(a) in acetonitrile both indicate that compound I should behave as a superbase. This has been confirmed by spectrophotometric titrations in MeCN using polyphosphazene references, which give an average pK(a) of 28.98 +/- 0.05. Triadic analysis indicates that the dominant term causing the high basicity is the relaxation energy.

To permit facile (15)N solid-state NMR (ssNMR) analysis of the degree of acetylation (DA) of chitinous materials in fungi a method for the introduction of a (15)N isotopic label has been developed. Using Penicillium chrysogenum as a model system, a series of (15)N-based media were surveyed for their abilities to support mycelial growth, and a rich medium supplemented with ((15)NH(4))(2)SO(4) supported good growth. Uptake of label into chitin extracted from mycelia grown in the rich ((15)NH(4))(2)SO(4)-based media was monitored by mass spectrometry, with approximately 1 g/L of ((15)NH(4))(2)SO(4) leading to approximately 65% incorporation. The labeled chitin was studied by ssNMR to determine its DA, and the (15)N label permitted measurement of DA to within 0.5% with acquisition times of on the order of half an hour. Similar studies validated the method for DA measurements on chitin from cultures of Aspergillus niger and Mucor rouxii.

A combined experimental/theoretical study provides insight into the bridging coordination of M-Cl bonds with the ambiphilic phosphine-borane ligands iPr(2)P-o(C(6)H(4))-BR(2) (PBCy(2): R = Cy; PBMes(2): R = Mes). Reaction of [PdCl(allyl)(PBCy(2))] (3) with HCl affords the related dinuclear complex [PdCl(mu-Cl)(PBCy(2))](2) (5). Subsequent cleavage of the chloride bridge by PPh(3) leads to the heteroleptic mononuclear complex trans-[PdCl(2)(PPh(3))(PBCy(2))] (6). The solid-state structures of complexes 5 and 6 substantiate the propensity of the PBCy(2) ligand to bridge Pd-Cl bonds via P-->Pd--Cl-->B interactions. DFT calculations carried out on both the model mononuclear complexes 3* and 6* reveal that in each system the energy of the linkage isomer with a Cl-->B interaction is very similar to that without. A comparison of the solution and solid-state (11)B NMR spectroscopic data for complexes 3 and 6 suggests the possible interconversion of the bridging and B-pendant forms in solution. Bridging coordination of the PBCy(2) ligand across a Rh-Cl bond is observed in the solid-state structure of the related complex [RhCl(nbd)(PBCy(2))] (7). Replacement of the Cy groups at boron by Mes substituents illustrates the role of steric factors on the participation of the Lewis acid upon coordination, no Cl-->B interaction being observed in the complex [PdCl(allyl)(PBMes(2))] (8).

The first enantiopure 4,4'-bipyridyls, , , and have been prepared in four or five steps via bacterial dioxygenase-catalysed cis-dihydroxylation of 4-chloroquinoline and C-C coupling; ligands and are found to be effective building blocks for the preparation of chiral metal-organic frameworks as demonstrated with the rational synthesis of two pillared-grid structures [Zn(2)(fumarate)(2)(L)], which exhibit interesting structural and dynamic aspects.

29Si NMR data have been recorded for the apatite series La8+xSr2-x(SiO4)6O2+x/2 (0 < or = x < or = 1.0). For x = 0, a single NMR peak is observed at a chemical shift of approximately -77 ppm, while as the La : Sr ratio and hence interstitial oxygen content is increased, a second peak at a chemical shift of approximately -80 ppm is observed, which has been attributed to silicate groups neighbouring interstitial oxide ions. An increase in the intensity of this second peak is observed with increasing x, consistent with an increase in interstitial oxide ion content, and the data are used to estimate the level of interstitial oxide ions, and hence Frenkel-type disorder in these materials. The increase in second 29Si NMR peak intensity/interstitial oxide ion content is also shown to correlate with an increase in conductivity. The effect of interstitial oxygen content can also be studied by means of Raman spectroscopy, with a new mode at 360 cm(-1) appearing for samples with x > 0 in the symmetric bending mode energy region of the SiO4 group. The intensity of this mode increases with increasing oxygen content, yielding results comparable to those from the NMR studies, showing the complementarities of the two techniques.

In this communication we report, for the first time, the ring-opening polymerisation in the melt of rac-lactide with heterogeneous catalysts. Homogeneous model systems based on silsesquioxanes have been prepared for comparison.

We report the synthesis, spectroscopic and structural characterization, and computational analysis of a series of phosphomolybdate complexes with tetravalent metal cations. The reaction between Ce (IV) and Th (IV) with phosphomolybdate at the optimum pH for the stabilization of the lacunary heteropolyoxometalate anion, [PMo 11O 39] (7-), results in the formation of compounds containing the anions [Ce(PMo 11O 39) 2] (10-) and [Th(PMo 11O 39) 2] (10-), respectively. Single crystal X-ray diffraction analysis was performed on salts of both species, Cs 10[Ce(PMo 11O 39) 2].20H 2O and (NH 4) 10[Th(PMo 11O 39) 2].22H 2O. In both anionic complexes the f-block metal cation is coordinated to the four unsaturated terminal lacunary site oxygens of each [PMo 11O 39] (7-) anion, yielding 8 coordinate sandwich complexes, analogous to previously prepared related complexes. Spectroscopic characterization points to the stability of these complexes in solution over a reasonably wide pH range. Density functional analysis suggests that the Ce-O bond strength in [Ce(PMo 11O 39) 2] (10-) is greater than the Th-O bond strength in [Th(PMo 11O 39) 2] (10-), with the dominant bonding interaction being ionic in both cases. In contrast, under similar reaction conditions, the dominant solid state Zr (IV) and Hf (IV) complexes formed contain the anions [Zr(PMo 12O 40)(PMo 11O 39)] (6-) and [Hf(PMo 12O 40)(PMo 11O 39)] (6-), respectively. In these complexes the central Group 4 d-block metal cations are coordinated to the four unsaturated terminal lacunary site oxygens of the [PMo 11O 39] (7-) ligand and to four bridging oxygens of a plenary Keggin anion, [PMo 12O 40] (3-). In addition, (NH 4) 5{Hf[PMo 12O 40][(NH 4)PMo 11O 39]}.23.5H 2O can be crystallized as a minor product. The structure of the anion, {Hf[PMo 12O 40][(NH 4)PMo 11O 39]} (5-), reveals coordination of the central Hf (IV) cation via four bridging oxygens on both the coordinated [PMo 11O 39] (7-) and [PMo 12O 40] (3-) anions. Unusually, the highly charged lacunary site remains uncoordinated to the Hf metal center but instead interacts with an ammonium cation. (31)P NMR indicates that complexation of the Keggin anion, [PMo 12O 40] (3-), to Hf (IV) and Zr (IV) will stabilize the Keggin anion to a much higher pH than usually observed.

A straightforward methodology for the high-yielding synthesis of the di-functionalised phosphines {Ph2P(CH2)2NC4H8E, E = NMe (1), O (2), S (3)}via base-catalysed Michael addition is described. Reaction of the functionalised tertiary phosphines 1-3 with PdCl2(MeCN)2 affords complexes in which the ligands are bound in a tridentate fashion, namely [PdCl(kappa3-PNE)]Cl (6a, 8) as the predominant products. A kappa2-PN coordination mode was also identified crystallographically for ligand following its reaction with PdCl2(MeCN)2, which afforded [PdCl2(-kappa2-PN)] (6b) in ca. 5% yield. Conductivity studies of solutions of 6a are consistent with an ionic formulation, however the poor solubility of and precluded their study in a similar fashion. Analysis of bulk samples of [PdCl2(1)] (6) and [PdCl2(3)] (8) by 15N and 31P NMR spectroscopy in the solid state as consistent with exclusive tridentate binding of the PNE ligands. An X-ray crystallographic study has probed the coordination of in the unusual salt [PdCl(-kappa3-PNN)]2[Mg(SO4)2(OH2)4] (10) prepared by treating a methanolic solution of with excess MgSO4. No data could be obtained to support the transformation of 6a into 6b on addition of excess chloride. In contrast, 6a reacts regioselectively with the water-soluble phosphine Cy2PCH2CH2NMe3Cl to afford the cis-diphosphine complex cis-[PdCl(Cy2PCH2CH2NMe3Cl)(1-kappa2-PN)]Cl2 (9). Reaction of 1 with PdCl(Me)(COD) results in the formation of the kappa2-PN dichloride complex [PdCl(Me)(1-kappa(2)-PN)] (11). Attempts to prepare [Pd(Me)(MeCN)(-kappa2-PN)][PF6] (12) through reaction of 11 with NaPF6 in MeCN led to decomposition. Treatment of PdMe2(TMEDA) with 1 at low temperature initially affords [PdMe2(1-kappa2-NN)], which isomerises to afford [PdMe(2)(1-kappa(2)-PN)] (13); at temperatures greater than 10 degrees C complex 13 decomposes rapidly.

We have characterised the stable polymorphic forms of two drug molecules, indomethacin (1) and nifedipine (2) by 13C CPMAS NMR and the resonances have been assigned. The signal for the C-Cl carbon of indomethacin has been studied as a function of applied magnetic field, and the observed bandshapes have been simulated. Variable-temperature 1H relaxation measurements of static samples have revealed a T1rho minimum for indomethacin at 17.8 degrees C. The associated activation energy is 38 kJ mol(-1). The relevant motion is probably an internal rotation and it is suggested that this involves the C-OCH3 group. Since the two drug compounds are potential candidates for formulation in the amorphous state, we have examined quench-cooled melts in detail by variable-temperature 13C and 1H NMR. There is a change in slope for T1H and T1rhoH at the glass transition temperature (Tg) for indomethacin, but this occurs a few degrees below Tg for nifedipine, which is perhaps relevant to the lower real-time stability of the amorphous form for the latter compound. Comparison of relaxation time data for the crystalline and amorphous forms of each compound reveals a greater difference for nifedipine than for indomethacin, which again probably relates to real-time stabilities. Recrystallisation of the two drugs has been followed by proton bandshape measurements at higher temperatures. It is shown that, under the conditions of the experiments, recrystallisation of nifedipine can be detected already at 70 degrees C, whereas this does not occur until 110 degrees C for indomethacin. The effect of crushing the amorphous samples has been studied by 13C NMR; nifedipine recrystallises but indomethacin does not. The results were supported by DSC, powder XRD, FTIR and solution-state NMR measurements., (Copyright (c) 2005 John Wiley & Sons, Ltd.)

The function of the arabinan and galactan side-chains of pectin remains unknown. We describe 13C NMR experiments designed to yield spectra from the most mobile polymer components of hydrated cell walls isolated from a range of plant species. In pectin-rich cell walls, these corresponded to the pectic side-chains. The arabinan side-chains were in general more mobile than the galactans, but the long galactan side-chains of potato pectin showed high mobility. Due to motional line-narrowing effects these arabinan and galactan chains gave 13C NMR spectra of higher resolution than has previously been observed from 'solid' biopolymers. These spectra were similar to those reported for the arabinan and galactan polymers in the solution state, implying time-averaged conformations resembling those found in solution. The mobility of the highly esterified galacturonan in citrus cell walls overlapped with the lower end of the mobility range characteristic of the pectic side-chains. The cellulose-rich cell walls of flax phloem fibres gave spectra of low intensity corresponding to mobile type II arabinogalactans. Cell walls from oat coleoptiles appeared to contain no polymers as mobile as the pectic arabinans and galactans in primary cell walls of the other species examined. These properties of the pectic side-chains suggest a role in interacting with water.

The crystallinity and amorphous content of a micronized pharmaceutical development drug substance have been independently determined. An evaluation of different techniques for this purpose has been carried out, and it was found that solid-state nuclear magnetic resonance (ss NMR) and X-ray powder diffraction (XRPD) were suitable for the former and latter, respectively. The baseline intensities of X-ray powder diffractograms, associated with the amorphous component of the sample, have been used to detect levels of non-crystalline material greater than 5%w/w with an absolute accuracy of +/-3%. ss NMR has been employed to quantify crystalline defects at levels of greater than 3%w/w with an estimated uncertainty of +/-2%. It is proposed that such crystalline defects arise from molecular conformational differences that only have a small effect on crystal lattice parameters and, by implication, only have small effects on X-ray powder diffractograms. In both cases the techniques are shown to be highly reproducible and require minimal sample preparation. Excellent linearity is demonstrated for the determination of amorphous material using prepared standards. The present account describes the choice of analytical method, method validation and the results obtained for typical samples of drug substance. It is demonstrated that solid-state NMR should be used as a complementary technique with respect to XRPD for studying crystallinity., ((c) 2005 Wiley-Liss, Inc.)

Molecular mobility and physical form of co-spray-dried sugar-lysozyme formulations were evaluated. Co-spray-dried trehalose:lysozyme and sucrose:lysozyme formulations in 1:9, 1:1 and 9:1 ratios (w:w) were stored at 0% RH and 75% RH for 5-6 days. Molecular mobility and physical form of the co-spray-dried formulations after storage were determined by using 13C and 1H solid-state NMR as well as X-ray powder diffractometry. The results showed that increasing sugar content in co-spray-dried formulations stored at 0% RH decreased molecular mobility of the amorphous formulations indicating a close association of the protein and sugar. Exposure of sugar-lysozyme 1:1 and 9:1 formulations to 75% RH led to separation of sugar and protein phases, where the sugar phase was crystalline. The intimate sugar-lysozyme interaction of the formulations stored at 0% RH and the phase separation of the sugar-rich formulations stored at 75% RH were also confirmed by using 13C solid-state NMR spin-lattice relaxation time-filter (T1-filter) measurements. The propensity of sucrose and trehalose to crystallise was similar; however, the results suggest that part of the sugar in the phase-separated formulations remained amorphous and in close association with lysozyme.

We report the syntheses and crystal structures of (NH4)11[Ln(III)(PMo11O39)2.xH2O (where Ln = every trivalent lanthanide cation except promethium) in which two lacunary [PMo11O39]7- anions sandwich an 8-coordinate Ln(III) cation to yield the complex anion, [LnIII(PMo11O39)2]11-. The 14 salts crystallise in two different space groups, C2/c or P1, but the LnIII containing anions are isostructural across the whole series, a very rare example of such a complete study. Solid state and solution 31P NMR, Raman and IR spectroscopies have been used to prove the stability of [Ln(PMo11O39)2]11- in aqueous solution. As expected, the LnIII cation contracts across the series and the Ln-O bond distances decrease uniformly. Interestingly, the splitting in the nu(P-O) mode within the [PMo11O39]7- unit increases uniformly across the series, which we attribute to the stronger interaction with the smaller, higher charge density LnIII cation as the series is traversed. For the 31P NMR measurements a direct comparison of Lanthanide Induced (paramagnetic) Shift could be made with the analogous [P(W11O39)2]11- complexes.