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1.
Dongshuang Wu Kohei Kusada Tomokazu Yamamoto Takaaki Toriyama Syo Matsumura Ibrahima Gueye Okkyun Seo Jaemyung Kim Satoshi Hiroi Osami Sakata Shogo Kawaguchi Yoshiki Kubota Hiroshi Kitagawa 《Chemical science》2020,11(47):12731
We report the synthesis of high-entropy-alloy (HEA) nanoparticles (NPs) consisting of five platinum group metals (Ru, Rh, Pd, Ir and Pt) through a facile one-pot polyol process. We investigated the electronic structure of HEA NPs using hard X-ray photoelectron spectroscopy, which is the first direct observation of the electronic structure of HEA NPs. Significantly, the HEA NPs possessed a broad valence band spectrum without any obvious peaks. This implies that the HEA NPs have random atomic configurations leading to a variety of local electronic structures. We examined the hydrogen evolution reaction (HER) and observed a remarkably high HER activity on HEA NPs. At an overpotential of 25 mV, the turnover frequencies of HEA NPs were 9.5 and 7.8 times higher than those of a commercial Pt catalyst in 0.05 M H2SO4 and 1.0 M KOH electrolytes, respectively. Moreover, the HEA NPs showed almost no loss during a cycling test and were much more stable than the commercial Pt catalyst. Our findings on HEA NPs may provide a new paradigm for the design of catalysts.RuRhPdIrPt high-entropy-alloy nanoparticles with a broad and featureless valence band spectrum show high hydrogen evolution reaction activity. 相似文献
2.
Direct Introduction of a Dimesitylboryl Group Using Base‐Mediated Substitution of Aryl Halides with Silyldimesitylborane 下载免费PDF全文
Dr. Eiji Yamamoto Kiyotaka Izumi Ryosuke Shishido Prof. Dr. Tomohiro Seki Noriaki Tokodai Prof. Dr. Hajime Ito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(49):17547-17551
The first dimesitylboryl substitution of aryl halides with a silylborane bearing a dimesitylboryl group in the presence of alkali‐metal alkoxides is described. The reactions of aryl bromides or iodides with Ph2MeSi?BMes2 and Na(OtBu) afforded the desired aryl dimesitylboranes in good to high yields and with high borylation/silylation ratios. Selective reaction of the sterically less‐hindered C?Br bond of dibromoarenes provided monoborylated products. This reaction was used to rapidly construct a D‐π‐A aryl dimesityl borane with a non‐symmetrical biphenyl spacer. 相似文献
3.
Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics 下载免费PDF全文
Prof. Dr. Soji Shimizu Taku Iino Prof. Dr. Akinori Saeki Prof. Dr. Shu Seki Prof. Dr. Nagao Kobayashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):2893-2904
Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved. 相似文献
4.
Controllable Electronic Structures and Photoinduced Processes of Bay‐Linked Perylenediimide Dimers and a Ferrocene‐Linked Triad 下载免费PDF全文
Haruki Horinouchi Dr. Hayato Sakai Prof. Yasuyuki Araki Prof. Tomo Sakanoue Prof. Taishi Takenobu Prof. Takehiko Wada Prof. Nikolai V. Tkachenko Prof. Taku Hasobe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9631-9641
A series of perylene‐3,4,9,10‐bis(dicarboximide) (PDI) dimers linked through the bay regions was systematically synthesized to examine the electronic structures and photophysical properties in dependence on the distance and orientation between the two PDI units. The spectroscopic and electrochemical measurements suggested that the coupling value of a directly linked PDI dimer (PDI)2 is much larger than those of para‐ and meta‐phenylene‐bridged PDI dimers p‐(PDI)2 and m‐(PDI)2. The width of Davydov splitting was quantitatively evaluated to compare the coupling values between the two PDI units in these dimers by absorption spectroscopy in frozen 2‐methyl‐THF. Excimer formation of PDI dimers induced the strong fluorescence quenching and large red‐shifts. Femtosecond transient absorption revealed a broad absorption derived from an excimer in the range from about 600 nm to the near‐IR region. The rate constants of formation and decay of the excimer are strongly dependent on the coupling values. Time‐resolved measurements on ferrocene‐linked p‐(PDI)2 revealed a competition between the photoinduced processes of electron transfer and excimer formation in PhCN, which is in sharp contrast with the sole electron‐transfer process in toluene. 相似文献
5.
Synthesis,Properties, and Redox Behavior of 1,1,4,4‐Tetracyano‐2‐ferrocenyl‐1,3‐butadienes Connected by Aryl,Biaryl, and Teraryl Spacers 下载免费PDF全文
Dr. Taku Shoji Akifumi Maruyama Chisa Yaku Natsumi Kamata Prof. Dr. Shunji Ito Dr. Tetsuo Okujima Prof. Dr. Kozo Toyota 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):402-409
Aryl‐substituted 1,1,4,4‐tetracyano‐1,3‐butadienes (FcTCBDs) and bis(1,1,4,4‐tetracyanobutadiene)s (bis‐FcTCBDs), possessing a ferrocenyl group on each terminal, were prepared by the reaction of a variety of alkynes with tetracyanoethylene (TCNE) in a [2+2] cycloaddition reaction, followed by retro‐electrocyclization of the initially formed [2+2] cycloadducts (i.e., cyclobutene derivatives). The characteristic intramolecular charge transfer (ICT) between the donor (ferrocene) and acceptor (TCBD) moieties were investigated by using UV/Vis spectroscopy. The redox behaviors of FcTCBDs and bis‐FcTCBDs were examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their properties of multi‐electron transfer depending on the number of ferrocene and TCBD moieties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions. 相似文献
6.
7.
Synthesis of a Pentacene‐Type Silaborin via Double Dehydrogenative Cyclization of 1,4‐Diboryl‐2,5‐disilylbenzene 下载免费PDF全文
Tatsuya Hirofuji Dr. Toshiaki Ikeda Prof. Dr. Takeharu Haino Prof. Dr. Yohsuke Yamamoto Prof. Dr. Atsushi Kawachi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9734-9739
A new pentacene‐type silaborin, in which three benzene rings are bridged by silicon and boron atoms, has been synthesized and characterized by using NMR spectroscopy and X‐ray crystallographic analysis. The precursor, 1,4‐bis(dimesitylboryl)‐2,5‐bis(phenylsilyl)benzene ( 4 ), was prepared by stepwise introduction of a silyl group and a boryl group to a benzene ring starting from 1,4‐dibromobenzene. Double cyclization of 4 proceeds by a H‐Mes exchange and a B‐H/C‐H dehydrogenative condensation to afford pentacene‐type silaborin 5 . X‐ray crystal structure analysis reveals that 5 adopts a bent structure rather than a planar one. UV/Vis spectra and DFT calculations for 5 reveal a lowering of the LUMO energy level compared with corresponding anthracene‐type 3 . 相似文献
8.
Yuki Shintani Taku Ohtomi Dr. Aya Shibata Dr. Yoshiaki Kitamura Koichiro M. Hirosawa Prof. Kenichi G. N. Suzuki Prof. Masato Ikeda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202104421
Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging. 相似文献
9.
Dr. Taku Kitanosono Prof. Dr. Shū Kobayashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9408-9429
Ever-evolving catalyst advances in synthetic protocols using water as a reaction medium have enriched the understanding of sustainable organic chemistry. Because conventional classification and definitions were ambivalent, it is proposed here that catalytic reactions using water be collectively called to be “in water”, with further classification into seven types. When accelerated in water as heterogeneous mixtures, the reactions can be regarded as following an “on-water” mechanism. The original term “on water” coined by Sharpless is incongruous with catalytic reactions, whereas on-water used in this review covers all the interfaces involving water where chemical reactions are accelerated. As a result of the unconcluded dispute on the antiquated catalyst-free “on water” model, the modified model defines three water layers: water molecules that are oriented to extrude protons toward the oil phase in the inner layer, those enwrapped by a secondary layer, and finally the bulk water layer. In light of the latitudinous outlook on the role of water at the interface, selected examples of reactions, in particular those reported over the past decade, that follow an “on-water” mechanism are reviewed herein. 相似文献
10.
Dr. Takeshi Matsumoto Risa Yamamoto Dr. Masanori Wakizaka Dr. Akinobu Nakada Prof. Dr. Ho-Chol Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9609-9619
The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H2) important. A high-spin (hs) FeII complex with o-phenylenediamine (opda) ligands, [FeII(opda)3]2+ (hs- [6R] 2+), was reported showing photochemical H2 evolution. In addition, a low-spin (ls) [FeII(bqdi)3]2+ (bqdi: o-benzoquinodiimine) (ls- [0R] 2+) formation by O2 oxidation of hs- [6R] 2+, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls- [0R] [PF6]2 can be reduced by hydrazine giving ls-[FeII(opda)(bqdi)2][PF6]2 (ls- [2R] [PF6]2) and ls-[FeII(opda)2(bqdi)][PF6]2 (ls- [4R] [PF6]2) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials. 相似文献