Liquid crystalline behaviours of some 3-perfluoroalkylbenzoate esters

A series of 3-perfluoroalkylbenzoate esters are synthesised. They tend to exhibit enantiotropic SmA and SmC phases. The clearing points are decreased with increasing the alkoxy chain length and show odd-even effect. With increasing the fluorocarbon chain length, the melting and clearing points increase; however, the SmC phase is suppressed.     

Novel tantalum phosphate Na13Sr2Ta2(PO4)9: synthesis,crystal structure,DFT calculations and Dy3+‐activated fluorescence performance

A new tantalum phosphate, tridecasodium distrontium ditantalum nonaphosphate, Na₁₃Sr₂Ta₂(PO₄)₉, was prepared using the high‐temperature flux method. The structure can be described as a three‐dimensional open framework containing isolated [Ta^V₂(PO₄)₉]¹⁷⁻ units that are interlocked by Na and Sr ions. Band structure studies by the first‐principles method revealed that Na₁₃Sr₂Ta₂(PO₄)₉ is an insulator with an indirect band gap of 4.78 eV, which makes it suitable as a luminescent host matrix. A series of solid solutions, i.e. Na₁₃Sr_2–xTa₂(PO₄)₉:xDy³⁺ (x = 0.01, 0.02, 0.04, 0.06, 0.08, 0.1, 0.12 and 0.14), were prepared and their photoluminescence properties studied. Under 350 nm light excitation, these emit two typical emissions of the Dy³⁺ ion, i.e. the ⁴F_9/2→⁶H_15/2 transition centred at 476 nm and the ⁴F_9/2→⁶H_13/2 transition centred at 570 nm.     

等离子体电极普克尔盒研究进展

等离子体电极普克尔盒(PEPC)用作多程放大控制、自激振荡抑制以及反激光隔离,是大型高功率固体激光器的核心器件。本文从高功率固体激光器的发展对光开关提出的要求出发,系统地综述了等离子体电极普克尔盒的性能特点以及研究进展。重点介绍了中国工程物理研究院激光聚变研究中心近年来在PEPC研究方面所取得的进展,包括单脉冲驱动的组合口径PEPC、低损耗PEPC以及重复频率运转的PEPC。     

Chiral one‐dimensional hydrogen‐bonded architectures constructed from single‐enantiomer phosphoric triamides

The two single‐enantiomer phosphoric triamides N‐(2,6‐difluorobenzoyl)‐N′,N′′‐bis[(S)‐(−)‐α‐methylbenzyl]phosphoric triamide, [2,6‐F₂‐C₆H₃C(O)NH][(S)‐(−)‐(C₆H₅)CH(CH₃)NH]₂P(O), denoted L‐1 , and N‐(2,6‐difluorobenzoyl)‐N′,N′′‐bis[(R)‐(+)‐α‐methylbenzyl]phosphoric triamide, [2,6‐F₂‐C₆H₃C(O)NH][(R)‐(+)‐(C₆H₅)CH(CH₃)NH]₂P(O), denoted D‐1 , both C₂₃H₂₄F₂N₃O₂P, have been investigated. In their structures, chiral one‐dimensional hydrogen‐bonded architectures are formed along [100], mediated by relatively strong N—H…O(P) and N—H…O(C) hydrogen bonds. Both assemblies include the noncentrosymmetric graph‐set motifs R₂²(10), R₂¹(6) and C₂²(8), and the compounds crystallize in the chiral space group P1. Due to the data collection of L‐1 at 120 K and of D‐1 at 95 K, the unit‐cell dimensions and volume show a slight difference; the contraction in the volume of D‐1 with respect to that in L‐1 is about 0.3%. The asymmetric units of both structures consist of two independent phosphoric triamide molecules, with the main difference being seen in one of the torsion angles in the OPNHCH(CH₃)(C₆H₅) part. The Hirshfeld surface maps of these levo and dextro isomers are very similar; however, they are near mirror images of each other. For both structures, the full fingerprint plot of each symmetry‐independent molecule shows an almost asymmetric shape as a result of its different environment in the crystal packing. It is notable that NMR spectroscopy could distinguish between compounds L‐1 and D‐1 that have different relative stereocentres; however, the differences in chemical shifts between them were found to be about 0.02 to 0.001 ppm under calibrated temperature conditions. In each molecule, the two chiral parts are also different in NMR media, in which chemical shifts and P–H and P–C couplings have been studied.     

Syntheses and structures of two novel fluorescent metal–organic frameworks generated from a tridentate donor–acceptor motif ligand

The tridentate organic ligand 4,4′,4′′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6,10‐triyl)tribenzoic acid ( H₃L ) has been synthesized (as the methanol 1.25‐solvate, C₄₈H₃₉NO₆·1.25CH₃OH). As a donor–acceptor motif molecule, H₃L possess strong intramolecular charge transfer (ICT) fluorescence. Through hydrogen bonds, H₃L molecules construct a two‐dimensional (2D) network, which pack together into three‐dimensional (3D) networks with an ABC stacking pattern in the crystalline state. Based on H₃L and M(NO₃)₂ salts (M = Cd and Zn) under solvothermal conditions, two metal–organic frameworks (MOFs), namely, catena‐poly[[triaquacadmium(II)]‐μ‐10‐(4‐carboxyphenyl)‐4,4′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6‐diyl)dibenzoato], [Cd(C₄₈H₃₇NO₆)(H₂O)₃]_n, I , and poly[[μ₃‐4,4′,4′′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6,10‐triyl)tribenzoato](μ₃‐hydroxido)zinc(II)], [Zn₂(C₄₈H₃₆NO₆)(OH)]_n, II , were synthesized. Single‐crystal analysis revealed that both MOFs adopt a 3D structure. In I , partly deprotonated HL ^2? behaves as a bidentate ligand to link a Cd^II ion to form a one‐dimensional chain. In the solid state of I , the existence of weak interactions, such as O—H…O hydrogen bonds and π–π interactions, plays an essential role in aligning 2D nets and 3D networks with AB packing patterns for I . The deprotonated ligand L ^3? in II is utilized as a tridentate building block to bind Zn^II ions to construct 3D networks, where unusual Zn₄O₁₄ clusters act as connection nodes. As a donor–acceptor molecule, H₃L exhibits fluorescence with a photoluminescence quantum yield (PLQY) of 70% in the solid state. In comparison, the PL of both MOFs is red‐shifted with even higher PLQYs of 79 and 85% for I and II , respectively.     

Synthesis,crystal structure and conformational analysis of an unexpected [1,5]dithiocine product of aminopyridine and thiovanillin

The condensation reaction of 2‐mercapto‐3‐methoxybenzaldehyde with 3‐aminopyridine afforded an unexpected N‐alkylated [1,5]dithiocine instead of the N‐salicylideneaniline. The proposed mechanism for this condensation involves a strong intramolecular hydrogen bond between the thiol and the amine groups, leading to a second condensation. The corresponding product, i.e. 4,10‐dimethoxy‐13‐(pyridin‐3‐yl)‐6H,12H‐6,12‐epiminodibenzo[b,f][1,5]dithiocine methanol 0.463‐solvate, C₂₁H₁₈N₂O₂S₂·0.463CH₃OH, was characterized by single‐crystal X‐ray diffraction analysis. The supramolecular structure shows π–π stacking and S…S interactions in the crystal packing. Within the asymmetric unit, two geometries of the N atom are observed. Although a planar geometry should be expected, a pyramidal one is observed due to the crystal packing. The presence of the two geometries was further supported by density functional theory (DFT) calculations that show an electronic energy difference of less than 2 kJ mol^?1 between the two conformers.     

Tolerance factor and phase stability of the garnet structure. Corrigendum

An error in an equation in the paper by Song et al. [ Acta Cryst. (2019), C 75 , 1353–1358 ] is corrected.     

Sulfono‐γ‐AApeptides as a New Class of Nonnatural Helical Foldamer

Foldamers offer an attractive opportunity for the design of novel molecules that mimic the structures and functions of proteins and enzymes including biocatalysis and biomolecular recognition. Herein we report a new class of nonnatural helical sulfono‐γ‐AApeptide foldamers of varying lengths. The crystal structure of the sulfono‐γ‐AApeptide monomer S6 illustrates the intrinsic folding propensity of sulfono‐γ‐AApeptides, which likely originates from the bulkiness of tertiary sulfonamide moiety. The two‐dimensional solution NMR spectroscopy data for the longest sequence S1 demonstrates a 10/16 right‐handed helical structure. Optical analysis using circular dichroism further supports well‐ defined helical conformation of sulfono‐γ‐AApeptides in solution containing as few as five building blocks. Future development of sulfono‐γ‐AApeptides may lead to new foldamers with discrete functions, enabling expanded application in chemical biology and biomedical sciences.     

Structure determination of KScS2, RbScS2 and KLnS2 (Ln = Nd,Sm, Tb,Dy, Ho,Er, Tm and Yb) and crystal–chemical discussion

The title structures of KScS₂ (potassium scandium sulfide), RbScS₂ (rubidium scandium sulfide) and KLnS₂ [Ln = Nd (potassium neodymium sufide), Sm (potassium samarium sulfide), Tb (potassium terbium sulfide), Dy (potassium dysprosium sulfide), Ho (potassium holmium sulfide), Er (potassium erbium sulfide), Tm (potassium thulium sulfide) and Yb (potassium ytterbium sulfide)] are either newly determined (KScS₂, RbScS₂ and KTbS₂) or redetermined. All of them belong to the α‐NaFeO₂ structure type in agreement with the ratio of the ionic radii r³⁺/r⁺. KScS₂, the member of this structural family with the smallest trivalent cation, is an extreme representative of these structures with rare earth trivalent cations. The title structures are compared with isostructural alkali rare earth sulfides in plots showing the dependence of several relevant parameters on the trivalent cation crystal radius; the parameters thus compared are c, a and c/a, the thicknesses of the S—S layers which contain the respective constituent cations, the sulfur fractional coordinates z(S²⁻) and the bond‐valence sums.     

Towards Polysulfuric Acids: The Hydrogentrisulfate Anion [HS3O10]− in A[HS3O10] (A=Na,K, Rb)

The reaction of Na₂SO₄ and K₂SO₄ with fuming sulfuric acid (65 % SO₃) yielded colorless extremely sensitive crystals of Na[HS₃O₁₀] (monoclinic; P2₁/n (No. 14); Z=4; a=707.36(2), b=1378.56(4), c=848.10(3) pm; β=94.817(1)°; V=824.09(4) ? 10⁶ pm³) and K[HS₃O₁₀] (orthorhombic; Pccn (No. 56); Z=4; a=1057.16(3), b=807.81(2), c=897.57(2) pm; V=766.51(3) ? 10⁶ pm³). The analogous rubidium compound Rb[HS₃O₁₀] (orthorhombic; Pnma (No. 62); Z=4; a=891.43(3), b=1095.34(4), c=839.37(3) pm; V=819.58(5) ? 10⁶ pm³) originates from the reaction of Rb₂CO₃ and SO₃. All of the different structures contain the hitherto unknown anion [HS₃O₁₀]^? and are stamped by strong hydrogen bonds linking the anions either to dimers or chains. Theoretical investigations by DFT methods give further insight in the structural characteristics of [HS₃O₁₀]^?. The preparation of the [HS₃O₁₀]^? anion can be seen as an important milestone on our way to the still elusive polysulfuric acids.