Structure-property relationship of a complex photoluminescent arylacetylide-gold(I) compound. I: a pressure-induced phase transformation caught in the act.

A pressure-induced triclinic-to-monoclinic phase transition has been caught `in the act over a wider series of high-pressure synchrotron diffraction experiments conducted on a large, photoluminescent organo-gold(I) compound. Here, we describe the mechanism of this single-crystal-to-single-crystal phase transition, the onset of which occurs at ∼0.6 GPa, and we report a high-quality structure of the new monoclinic phase, refined using aspherical atomic scattering factors. Our case illustrates how conducting a fast series of diffraction experiments, enabled by modern equipment at synchrotron facilities, can lead to overestimation of the actual pressure of a phase transition due to slow transformation kinetics

Multiple polar and non‐polar nematic phases.

Liquid-crystal materials exhibiting up to three nematic phases are reported. Dielectric response measurements show that while the lower temperature nematic phase has ferroelectric order and the highest temperature nematic phase is apolar, the intermediate phase has local antiferroelectric order. The modification of the molecular structure by increasing the number of lateral fluorine substituents leads to one of the materials showing a direct isotropic-ferronematic phase transition

The Doping Effect of Fluorinated Aromatic Solvent on the Rate of Ruthenium Catalysed Olefin Metathesis

A study concerning the effect of using a fluorinated aromatic solvent as the medium for olefin metathesis reactions catalysed by ruthenium complexes bearing N-heterocyclic carbene ligands is presented. The use of fluorinated aromatic hydrocarbons (FAH) as solvents for olefin metathesis reactions catalysed by standard commercially available ruthenium pre-catalysts allows substantially higher yields of the desired products to be obtained,especially in the case of demanding polyfunctional molecules, including natural and biologically active compounds. Interactions between the FAH and the second-generation ruthenium catalysts, which apparently improve the efficiency of the olefin metathesis transformation, have been studied by X-ray structure analysis and computations, as well as by carrying out a number of metathesis experiments. The optimisation of reaction conditions by using an FAH can be regarded as a complementary approach for the design of new improved ruthenium catalysts. Fluorinated aromatic solvents are an attractive alternative medium for promoting challenging olefin metathesis reactions

Intrinsically chiral ferronematic liquid crystals : An inversion of the helical twist sense at the chiral nematic – Chiral ferronematic phase transition

Funding Information: The research was supported by the National Science Centre (Poland) under the grant no. 2016/22/A/ST5/00319. C.T.I. and J.M.D.S. acknowledge the financial support of the Engineering and Physical Sciences Research Council [EP/V048775/1].Peer reviewedPostprin

Highly Fluorescent Dyes Containing Conformationally Restrained Pyrazolylpyrene (Pyrazoolympicene) Chromophore

The triflic-acid-promoted cyclization of 1-phenyl-3-(pyren-1-yl)-1H-pyrazole-4-carbaldehyde afforded a mixture of 9-phenyl-7,9-dihydropyreno (10,1-fg)indazole and 9-phenylpyreno(10,1-fg)indazole-7(9H)-one, readily separable by column chromatography. Both products contained a rigid six-ringed pyrazoolympicene backbone and exhibited bright fluorescence in chloroform solution and a weak fluorescence in the solid state. DFT and TD DFT calculations revealed that the lowest excited state (S1) of these compounds is populated via HOMO →LUMO π-π * transition. Furthermore, the synthesized compounds behaved as weak bases and their emission spectra showed substantial changes upon protonation. Therefore, they may be of interest for sensing of strongly acidic fluorophore environments

Pressure-Dependent Structural and Luminescence Properties of 1-(Pyren-1-yl)but-2-yn-1-one

The crystal structure of 1-(pyren-1-yl)but-2-yn-1-one ( 1 a , a polynuclear aromatic hydrocarbon displaying enhanced luminescence in the solid state, has been re-determined at several pressures ranging from atmospheric up to 3 GPa using a Diamond Anvil Cell (DAC). These experiments were augmented by periodic DFT calculations at pressures up to 4.4 GPa. UV-Vis fluorescence of 1 a at non-ambient pressures has also been investigated. The crystal structure consists of infinite π -stacks of anti-parallel 1 a molecules with discernible dimers, which may exemplify aggregates formed by pyrene derivatives in solution and thin films, and is predominantly stabilized by dispersion. The average inter-planar distance between individual molecules within π -stacks decreases with pressure in the investigated range. This results in piezochromic properties of 1 a : a red-shift of sample color, as well as a bathochromic shift of fluorescence with pressure (by ca. 100 nm at 3.5 GPa). Two-component fluorescence spectra support the hypothesis that at least two types of excimers are involved in the electronic excitation processes in crystalline 1 a

Regioselective (thio)carbamoylation of 2,7-di-tert-butylpyrene at the 1-position with iso(thio)cyanates

It has been found that 2,7-di-tert-butylpyrene reacts with aliphatic iso(thio)cyanates in the presence of trifluoromethanesulfonic acid to exclusively afford the corresponding 1-substituted (thio)amides in high yields. For aromatic iso(thio)cyanates the reaction is less regioselective, although substitution at the 1-position prevails. For ethoxycarbonyl isothiocyanate, apart from the 1-substituted thioamide, 1,8-disubstituted thioamide and 2,7-di-tert-butylpyrene-1-carbonitrile are formed (especially at longer reaction times)

Applied Crystallography The LaueUtil toolkit for Laue photocrystallography. I. Rapid orientation matrix determination for intermediate-size-unit-cell Laue data

A new method for determination of the orientation matrix of Laue X-ray data is presented. The method is based on matching of the experimental patterns of central reciprocal lattice rows projected on a unit sphere centered on the origin of the reciprocal lattice with the corresponding pattern of a monochromatic data set on the same material. This technique is applied to the complete data set and thus eliminates problems often encountered when single frames with a limited number of peaks are to be used for orientation matrix determination. Application of the method to a series of Laue data sets on organometallic crystals is described. The corresponding program is available under a Mozilla Public License-like open-source license

Crystal structure, interaction energies and experimental electron density of the popular drug ketoprophen

The crystal and molecular structure of the pure (S)-enantiomer of the popular analgesic and anti-inflammatory drug ketoprophen (α-ket) is reported. A detailed aspherical charge-density model based on high-resolution X-ray diffraction data has been refined, yielding a high-precision geometric description and classification of the O—H...O interactions as medium strength hydrogen bonds. The crystal structure of the racemic form of ketoprophen (β-ket) was also redetermined at 100 K, at 0.5 Å resolution. A previously unreported disorder (10% occupancy) was discovered. In contrast to the racemic β-ket case, the (S)-enantiomer crystallizes with two independent molecules in the asymmetric unit with two distinct conformations. The major difference between the β-ket and α-ket crystal forms lies in the formation of distinct hydrogen-bonded motifs: a closed ring motif in β-ket versus infinite chains of hydrogen bonds in the chiral α-ket structure. However, the overall crystal packing of both forms is surprisingly similar, with close-packed layers of antiparallel-oriented benzophenone moieties bound by C—H...π interactions. Notably, the most important stabilizing term in the total lattice energies in both instances proved to be the dispersion related to these interactions. Both forms of the title compound (α- and β-ket) were additionally characterized by differential scanning calorimetry and thermogravimetric analysis