Zigzag-Elongated Fused π-Electronic Core: A Molecular Design Strategy to Maximize Charge-Carrier Mobility

Printed and flexible electronics requires solution‐processable organic semiconductors with a carrier mobility (μ) of ≈10 cm2 V−1 s−1 as well as high chemical and thermal durability. In this study, chryseno[2,1‐b:8,7‐b′]dithiophene (ChDT) and its derivatives, which have a zigzag‐elongated fused π‐electronic core (π‐core) and a peculiar highest occupied molecular orbital (HOMO) configuration, are reported as materials with conceptually new semiconducting π‐cores. ChDT and its derivatives are prepared by a versatile synthetic procedure. A comprehensive investigation reveals that the ChDT π‐core exhibits increasing structural stability in the bulk crystal phase, and that it is unaffected by a variation of the transfer integral, induced by the perpetual molecular motion of organic materials owing to the combination of its molecular shape and its particular HOMO configuration. Notably, ChDT derivatives exhibit excellent chemical and thermal stability, high charge‐carrier mobility under ambient conditions (μ ≤ 10 cm2 V−1 s−1), and a crystal phase that is highly stable, even at temperatures above 250 °C

Selective photoinduced charge separation in perylenediimide-pillar[5]arene rotaxanes

The ability to control photoinduced charge transfer within molecules represents a major challenge requiring precise control of the relative positioning and orientation of donor and acceptor groups. Here we show that such photoinduced charge transfer processes within homo- and hetero-rotaxanes can be controlled through organisation of the components of the mechanically interlocked molecules, introducing alternative pathways for electron donation. Specifically, studies of two rotaxanes are described: a homo[3]rotaxane, built from a perylenediimide diimidazolium rod that threads two pillar[5]arene macrocycles, and a hetero[4]rotaxane in which an additional bis(1,5-naphtho)-38-crown-10 (BN38C10) macrocycle encircles the central perylenediimide. The two rotaxanes are characterised by a combination of techniques including electron diffraction crystallography in the case of the hetero[4]rotaxane. Cyclic voltammetry, spectroelectrochemistry, and EPR spectroscopy areemployed to establish the behaviour of the redox states of both rotaxanes and these data are used to inform photophysical studies using time-resolved infra-red (TRIR) and transient absorption (TA) spectroscopies. The latter studies illustrate the formation of a symmetrybreaking charge-separated state in the case of the homo[3]rotaxane in which charge transfer between the pillar[5]arene and perylenediimide is observed involving only one of the twomacrocyclic components. In the case of the hetero[4]rotaxane charge separation is observed involving only the BN38C10 macrocycle and the perylenediimide leaving the pillar[5]arene components unperturbed

High Performance Oxygen-bridged N-shaped Semiconductors with Stabilized Crystal Phase and Blue Luminescence

Here, we describe an oxygen-bridged N-shaped π-electron core, dinaphtho[2,3-d:2\u27,3\u27-d"]benzo[1,2-b:4,5-b\u27]difuran (DNBDF), as a new entity of organic semiconducting materials. Interestingly, by introduction of flexible alkyl chains at appropriate positions, DNBDF π-cores exhibit solution processability, a highly stabilized crystal phase, high mobility, and blue luminescence as a solid.平成26年度関西大学若手研究者育成経費JSPS科学研究費補助金　若手研究(B)(No.25810118)JSPS科学研究費補助金　基盤研究(C)(No.26410254)JSPS科学研究費補助金　基盤研究(B)(No.25288091

Understanding the solid-state structure of riboflavin through a multitechnique approach

Crystalline riboflavin (vitamin B2) performs an important biological role as an optically functional material in the tapetum lucidum of certain animals, notably lemurs and cats. The tapetum lucidum is a reflecting layer behind the retina, which serves to enhance photon capture and vision in low-light settings. Motivated by the aim of rationalizing its biological role, and given that the structure of biogenic solid-state riboflavin remains unknown, we have used a range of experimental and computational techniques to determine the solid-state structure of synthetic riboflavin. Our multitechnique approach included microcrystal XRD, powder XRD, three-dimensional electron diffraction (3D-ED), high-resolution solid-state 13C NMR spectroscopy, and dispersion-augmented density functional theory (DFT-D) calculations. Although an independent report of the crystal structure of riboflavin was published recently, our structural investigations reported herein provide a different interpretation of the intermolecular hydrogen-bonding arrangement in this material, supported by all the experimental and computational approaches utilized in our study. We also discuss, more generally, potential pitfalls that may arise in applying DFT-D geometry optimization as a bridging step between structure solution and Rietveld refinement in the structure determination of hydrogen-bonded materials from powder XRD data. Finally, we report experimental and computational values for the refractive index of riboflavin, with implications for its optical function

Andersson‐Magnéli phases TinO2n‐1: recent progress inspired by Swedish scientists

l conductivity and chemical/thermal stability. Various applications have also been reported for the phases with different values of n, or slightly reduced rutile (TiO2). The characteristic properties of these materials depend strongly on the compositional deviation from TiO2 and the way in which the structure accommodates the deviation. Thus, an urgent requirement is to overcome difficulties in characterizing such materials at atomic resolution. Here, we trace the discovery of the Andersson‐Magnéli phases, and report the application of recent developments in electron microscopy to reveal the relation, at the local level, between structural characteristics and electronic states, specifically for the materials TinO2n‐1 with n=4–8. The electrical conductivity of Ti4O7 has been reported previously to show three clearly distinct states on decreasing temperature from 300 K. For this reason, we focus on Ti4O7 as a representative example of the TinO2n‐1 phases and report structural characteristics at temperatures corresponding to each of the three different phases, focusing on the distribution of Ti3+ and Ti4+ cations from analysis of single‐crystal XRD data. Electron diffraction experiments and electrical conductivity measurements are also reported

Building-block architecture of botulinum toxin complex: Conformational changes provide insights into the hemagglutination ability of the complex

Clostridium botulinum produces the botulinum neurotoxin (BoNT). Previously, we provided evidence for the “building-block” model of botulinum toxin complex (TC). In this model, a single BoNT is associated with a single nontoxic nonhemagglutinin (NTNHA), yielding M-TC; three HA-70 molecules are attached and form M-TC/HA-70, and one to three “arms” of the HA-33/HA-17 trimer (two HA-33 and one HA-17) further bind to M-TC/HA-70 via HA-17 and HA-70 binding, yielding one-, two-, and three-arm L-TC. Of all TCs, only the three-arm L-TC caused hemagglutination. In this study, we determined the solution structures for the botulinum TCs using small-angle X-ray scattering (SAXS). The mature three-arm L-TC exhibited the shape of a “bird spreading its wings”, in contrast to the model having three “arms”, as revealed by transmission electron microscopy. SAXS images indicated that one of the three arms of the HA-33/HA-17 trimer bound to both HA-70 and BoNT. Taken together, these findings regarding the conformational changes in the building-block architecture of TC may explain why only three-arm L-TC exhibited hemagglutination

Light-Induced Nucleation of Metastable Hen Egg-White Lysozyme Solutions

International audienc

Revised Stereochemistry of Ceramide-Trafficking Inhibitor HPA-12 by X‑ray Crystallography Analysis

In response to Berkeš’s report revising the stereochemistry of HPA-12, an important ceramide-trafficking inhibitor that was discovered and synthesized and its stereochemistry determined in 2001, the synthesis and the stereochemistry were reinvestigated. A large-scale synthetic method for HPA-12 based on a Zn-catalyzed asymmetric Mannich-type reaction in water was developed. Single crystals of HPA-12 for X-ray crystallographic analysis were obtained from ethyl propionate/<i>n</i>-hexane, and the stereochemistry was definitely determined to be 1<i>R</i>,3<i>S</i>, consistent with Berkeš’s revised structure

Structure determination of small molecule compounds by an electron diffractometer for 3D ED/MicroED

3D electron diffraction (3D ED)/Micro electron diffraction (MicroED) has extended the limits of crystallography by enabling the determination of three dimensional molecular structures from sub-μm microcrystals. However, 3D ED/microED measurements using current state-of-the-art electron microscopes require experts in both electron microscopy and crystallography making the method rather difficult for researchers who simply need structures. Here, we present a diffractometer specifically designed for 3D ED/microED and show how it works for determining crystal structures. The newly developed electron diffractometer will provide many researchers with an easy path to structure determination of crystals that are less than 1 μm in size