J. Appl. Cryst.の発刊に際して

Constructing highly planar, extended π-electron systems is an important strategy for achieving high-mobility organic semiconductors. In general, there are two synthetic strategies for achieving π-conjugated systems with high planarity. The conventional strategy connects neighboring aromatic rings through covalent bonds to restrict the rotation about single bonds. However, this usually requires a complex sequence of synthetic steps to achieve this target, which can be costly and labor-intensive. More recently, noncovalent through-space intramolecular interactions, which are defined here as noncovalent conformational locks, have been employed with great success to increase the planarity and rigidity of extended π-electron systems; this has become a well-known and important strategy to design and synthesize highly planar π-conjugated systems for organic electronics. This review offers a comprehensive and general summary of conjugated systems with such noncovalent conformational locks, including O···S, N···S,...

Organic and Polymeric Semiconductors Enhanced by Noncovalent Conformational Locks.

This review addresses the most relevant aspects of vibrational spectroscopies (IR, Raman and INS) applied to zeolites and zeotype materials. Surface Bronsted and Lewis acidity and surface basicity are treated in detail. The role of probe molecules and the relevance of tuning both the proton affinity and the steric hindrance of the probe to fully understand and map the complex site population present inside microporous materials are critically discussed. A detailed description of the methods needed to precisely determine the IR absorption coefficients is given, making IR a quantitative technique. The thermodynamic parameters of the adsorption process that can be extracted from a variable-temperature IR study are described. Finally, cutting-edge space- and time-resolved experiments are reviewed. All aspects are discussed by reporting relevant examples. When available, the theoretical literature related to the reviewed experimental results is reported to support the interpretation of the vibrational spectra on an atomic level.

/pdf/probing-zeolites-by-vibrational-spectroscopies-2g5hyjm2fr.pdf

Probing zeolites by vibrational spectroscopies

Indigo and its derivatives are dyes and pigments with a long and distinguished history in organic chemistry. Recently, applications of this 'old' structure as a functional organic building block for organic electronics applications have renewed interest in these molecules and their remarkable chemical and physical properties. Natural-origin indigos have been processed in fully bio-compatible field effect transistors, operating with ambipolar mobilities up to 0.5 cm(2) /Vs and air-stability. The synthetic derivative isoindigo has emerged as one of the most successful building-blocks for semiconducting polymers for plastic solar cells with efficiencies > 5%. Another isomer of indigo, epindolidione, has also been shown to be one of the best reported organic transistor materials in terms of mobility (∼2 cm(2) /Vs) and stability. This progress report aims to review very recent applications of indigoids in organic electronics, but especially to logically bridge together the hereto independent research directions on indigo, isoindigo, and other materials inspired by historical dye chemistry: a field which was the root of the development of modern chemistry in the first place.

25th anniversary article: progress in chemistry and applications of functional indigos for organic electronics.

The intense interactions of guest molecules with the pore walls of nanoporous materials is the subject of continued fundamental research Stimulated by their thermal energy, the guest molecules in these materials are subject to a continuous, irregular motion, referred to as diffusion Diffusion, which is omnipresent in nature, influences the efficacy of nanoporous materials in reaction and separation processes The recently introduced techniques of microimaging by interference and infrared microscopy provide us with a wealth of information on diffusion, hitherto inaccessible from commonly used techniques Examples include the determination of surface barriers and the sticking coefficient's analogue, namely the probability that, on colliding with the particle surface, a molecule may continue its diffusion path into the interior Microimaging is further seen to open new vistas in multicomponent guest diffusion (including the detection of a reversal in the preferred diffusion pathways), in guest-induced phase transitions in nanoporous materials and in matching the results of diffusion studies under equilibrium and non-equilibrium conditions

Microimaging of transient guest profiles to monitor mass transfer in nanoporous materials

Good-quality single crystals of the title compound, indigo B [systematic name: 2-(3-oxoindolin-2-yl­idene)indolin-3-one], C16H10N2O2, have been prepared with high selectivity by a sublimation process. The previous structure of indigo B [Susse & Wolf (1980). Naturwissenschaften, 67, 453], which showed that the complete mol­ecule is generated by crystallographic inversion symmetry has been confirmed, but the present study reports more realistic geometrical parameters and modern standards of precision (e.g. σ for C—C bonds = 0.002–0.003 A). Each mol­ecule features two intra­molecular N—H⋯O hydrogen bonds. In the crystal, mol­ecules are linked by strong face-to-face π–π stacking inter­actions involving both the six- and five-membered rings [centroid–centroid separations = 3.6290 (14) and 3.6506 (14) A] and inter­molecular N—H⋯O hydrogen bonds.

https://journals.iucr.org/e/issues/2011/11/00/hb6323/hb6323.pdf

Selective crystallization of indigo B by a modified sublimation method and its redetermined structure

Large crystals of all-silica, aluminum-, and boron-containing ferrierite zeolites were synthesized using a solvothermal synthesis method and a fluoride medium. Alkylamines, namely, propylamine, butylamine, and pentylamine were employed as templates in the syntheses. The products were characterized by powder X-ray diffraction (XRD), inductively coupled plasma-optical emission spectrometry (ICP-OES), thermogravimetric analysis (TGA), elemental (CHN) analyses, scanning electron microscopy (SEM), N2-adsorption, and 1H, 11B, 27Al, as well as 29Si MAS NMR spectroscopy. The 27Al and 11B MAS NMR spectroscopic investigations revealed that aluminum and boron were successfully incorporated into the FER-type framework. SEM indicated the occurrence of crystals with a size of up to about 600 μm. Furthermore, for all-silica and boron-containing ferrierite zeolites, the shape, size, and thickness of the crystals could be controlled by increasing the chain length of the alkyl group in the alkylamine and the crystallizatio...

Solvothermal Synthesis and Characterization of Large-Crystal All-Silica, Aluminum-, and Boron-Containing Ferrierite Zeolites

A series of isostructural 3D coordination polymers 3∞[M(tdc)(bpy)] (M2+ = Zn2+, Cd2+, Co2+, Fe2+; tdc2– = 2,5-thiophenedicarboxylate; bpy = 4,4′-bipyridine) was synthesized and characterized by X-r...

Synthesis, crystal structure and catalytic behavior of homo- and heteronuclear coordination polymers [M(tdc)(bpy)] (M2+ = Fe2+, Co2+, Zn2+, Cd2+; tdc2- = 2,5-thiophenedicarboxylate).

Tuning the catalytic activity of the heteronuclear coordination polymers [CoxZn1 − x(tdc)(bipy)] and [CoxZn1 − x(Me2trz–pba)2] in the epoxidation of cyclooctene via isomorphous substitution

With 1,1′-cobaltocenium dicarboxylate as a cobalt-containing linker, heteronuclear coordination polymers 2∞[M(ccdc)2] (M2+ = Zn2+, Cd2+, Cu2+; ccdc− = 1,1′-cobaltocenium dicarboxylate) are generated. These compounds exhibit symmetry related structures with their structural details depending on the preferred coordination sphere of the respective metal ion. The structural relationships between these two-dimensional coordination polymers and the dependence on type and quantity of cocrystallized solvent molecules are discussed in this article. In the presence of 4,4′-bipyridine (bipy) as a co-linker, metal acetates and Hccdc/(H2ccdc)PF6 form the three-dimensional framework 3∞[Zn(ccdc)(bipy)]PF6 and the two-dimensional networks 2∞[Zn(ccdc)(bipy)]PF6 and 2∞[Cu(ccdc)(bipy)]PF6.

Florian Kettner

Papers

Selective crystallization of indigo B by a modified sublimation method and its redetermined structure

Solvothermal Synthesis and Characterization of Large-Crystal All-Silica, Aluminum-, and Boron-Containing Ferrierite Zeolites

Synthesis, crystal structure and catalytic behavior of homo- and heteronuclear coordination polymers [M(tdc)(bpy)] (M2+ = Fe2+, Co2+, Zn2+, Cd2+; tdc2- = 2,5-thiophenedicarboxylate).

Tuning the catalytic activity of the heteronuclear coordination polymers [CoxZn1 − x(tdc)(bipy)] and [CoxZn1 − x(Me2trz–pba)2] in the epoxidation of cyclooctene via isomorphous substitution

Coordination polymers based on 1,1′-cobaltocenium dicarboxylate linkers