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Caitlin E. Shields Dr. Xue Wang Dr. Thomas Fellowes Rob Clowes Dr. Linjiang Chen Prof. Graeme M. Day Prof. Anna G. Slater Dr. John W. Ward Dr. Marc A. Little Prof. Andrew I. Cooper 《Angewandte Chemie (International ed. in English)》2023,62(34):e202303167
Hydrogen-bonded organic frameworks (HOFs) with low densities and high porosities are rare and challenging to design because most molecules have a strong energetic preference for close packing. Crystal structure prediction (CSP) can rank the crystal packings available to an organic molecule based on their relative lattice energies. This has become a powerful tool for the a priori design of porous molecular crystals. Previously, we combined CSP with structure-property predictions to generate energy-structure-function (ESF) maps for a series of triptycene-based molecules with quinoxaline groups. From these ESF maps, triptycene trisquinoxalinedione (TH5) was predicted to form a previously unknown low-energy HOF (TH5-A) with a remarkably low density of 0.374 g cm−3 and three-dimensional (3D) pores. Here, we demonstrate the reliability of those ESF maps by discovering this TH5-A polymorph experimentally. This material has a high accessible surface area of 3,284 m2 g−1, as measured by nitrogen adsorption, making it one of the most porous HOFs reported to date. 相似文献
13.
Dr. Samuel C. Scott Dr. Jamie A. Cadge Grace K. Boden Prof. John F. Bower Dr. Christopher A. Russell 《Angewandte Chemie (International ed. in English)》2023,62(23):e202301526
We describe a AuI complex of a hemi-labile (C^N) N-heterocyclic carbene ligand that is able to mediate oxidative addition of aryl iodides. Detailed computational and experimental investigations have been undertaken to verify and rationalize the oxidative addition process. Application of this initiation mode has resulted in the first examples of “exogenous oxidant-free” AuI/AuIII catalyzed 1,2-oxyarylations of ethylene and propylene. These demanding yet powerful processes establish these commodity chemicals as nucleophilic-electrophilic building blocks in catalytic reaction design. 相似文献
14.
Tuning the energy gap of conjugated polymer zwitterions for efficient interlayers and solar cells 下载免费PDF全文
Zachariah A. Page Feng Liu Thomas P. Russell Todd Emrick 《Journal of polymer science. Part A, Polymer chemistry》2015,53(2):327-336
Narrow band gap conjugated polymer zwitterions (CPZs) were synthesized by Suzuki polymerization and characterized to understand their electronic properties and utility as cathode modification layers in solar cells. The polymers were prepared from diketopyrrolopyrrole (DPP) and iso-indigo monomers containing sulfobetaine (SB) pendant groups, benefiting from an ion-rich aqueous phase in the polymerizations. UV–vis absorption spectroscopy revealed the optical energy gap value for the CPZs, ranging from 1.7 to 1.2 eV. Ultraviolet photoelectron spectroscopy of the CPZs as thin layers on Ag metal showed that the pendent zwitterions impart an interfacial dipole (Δ) to the metal and a work function reduction of ∼0.9 eV. OPVs fabricated using a conventional bulk heterojunction (BHJ) device architecture of ITO/PEDOT:PSS/(PTB7:PC71BM)/CPZ/Ag led to dramatic improvements in power conversion efficiency (PCE) values relative to devices having bare Ag cathodes (PCE < 2% for bare Ag vs. 6.7–7.7% for CPZ/Ag). The benzothiadiazole (BT)/DPP polymer denoted as PT2BTDPPSB gave an optimal PCE of 7.7% in a conventional BHJ OPV device architecture fabricated on a Ag cathode. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 327–336 相似文献
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Björn Bohman Gavin R. Flematti Russell A. Barrow 《Journal of mass spectrometry : JMS》2015,50(8):987-993
Pyrazines are well‐known natural products that are present in bacterial odours and food flavouring agents and are used as insect pheromones. Recently, a number of hydroxymethylpyrazines have been identified as thynnine wasp pheromones and orchid semiochemicals that are essential for pollination in sexually deceptive plants. These compounds are present in low amounts in complex blends, making GC–MS (including high‐resolution techniques) the method of choice for their structure elucidation. We report the EI mass spectra for 14 representative compounds and have found that based on characteristic fragmentations, it is possible to distinguish between different positional isomers of hydroxymethylpyrazines. The presence or absence of either [M ? 17]+, [M ? 18]+· or [M ? 19]+ fragment species provides characteristic information to allow the distinction between the different isomers. Considering the importance of pyrazines as a group of bioactive natural products, and the recent findings of biological activity for hydroxymethylpyrazines, our results presented here will aid the identification of these compounds in other biological systems. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
17.
Prof. Dr. Robin B. Bedford John G. Bowen Russell B. Davidson Dr. Mairi F. Haddow Annabelle E. Seymour‐Julen Dr. Hazel A. Sparkes Dr. Ruth L. Webster 《Angewandte Chemie (International ed. in English)》2015,54(22):6591-6594
Palladium(II) acetate is readily converted into [Pd3(μ2‐OH)(OAc)5] ( 1 ) in the presence of water in a range of organic solvents and is also slowly converted in the solid state. Complex 1 can also be formed in nominally anhydrous solvents. Similarly, the analogous alkoxide complexes [Pd3(μ2‐OR)(OAc)5] ( 3 ) are easily formed in solutions of palladium(II) acetate containing a range of alcohols. An examination of a representative Wacker‐type oxidation shows that the Pd‐OH complex 1 and a related Pd‐oxo complex 4 can be excluded as potential catalytic intermediates in the absence of exogenous water. 相似文献
18.
Dr. Aleksander Rebane Geoffrey Wicks Dr. Mikhail Drobizhev Dr. Thomas Cooper Aleksander Trummal Dr. Merle Uudsemaa 《Angewandte Chemie (International ed. in English)》2015,54(26):7582-7586
We present a new approach for determining the strength of the dipolar solute‐induced reaction field, along with the ground‐ and excited‐state electrostatic dipole moments and polarizability of a solvated chromophore, using exclusively one‐photon and two‐photon absorption measurements. We verify the approach on two benchmark chromophores N,N‐dimethyl‐6‐propionyl‐2‐naphthylamine (prodan) and coumarin 153 (C153) in a series of toluene/dimethyl sulfoxide (DMSO) mixtures and find that the experimental values show good quantitative agreement with literature and our quantum‐chemical calculations. Our results indicate that the reaction field varies in a surprisingly broad range, 0–107 V cm?1, and that at close proximity, on the order of the chromophore radius, the effective dielectric constant of the solute–solvent system displays a unique functional dependence on the bulk dielectric constant, offering new insight into the close‐range molecular interaction. 相似文献
19.
Dr. Lucy Clark Dr. Farida H. Aidoudi Dr. Cameron Black Dr. Kasun S. A. Arachchige Prof. Dr. Alexandra M. Z. Slawin Prof. Dr. Russell E. Morris Prof. Dr. Philip Lightfoot 《Angewandte Chemie (International ed. in English)》2015,54(51):15457-15461
The ionothermal synthesis, structure, and magnetic susceptibility of a novel inorganic–organic hybrid material, imidazolium vanadium(III,IV) oxyfluoride [C3H5N2][V9O6F24(H2O)2] (ImVOF) are presented. The structure consists of inorganic vanadium oxyfluoride slabs with kagome layers of V4+ S=${{ 1/2 }}$ ions separated by a mixed valence layer. These inorganic slabs are intercalated with imidazolium cations. Quinuclidinium (Q) and pyrazinium (Pyz) cations can also be incorporated into the hybrid structure type to give QVOF and PyzVOF analogues, respectively. The highly frustrated topology of the inorganic slabs, along with the quantum nature of the magnetism associated with V4+, means that these materials are excellent candidates to host exotic magnetic ground states, such as the highly sought quantum spin liquid. Magnetic susceptibility measurements of all samples suggest an absence of conventional long‐range magnetic order down to 2 K despite considerable antiferromagnetic exchange. 相似文献
20.
Stephen P. Cooper Kevin I. Booker‐Milburn 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(22):6596-6600
Polyheterocycles are found in many natural products and are useful moieties in functional materials and drug design. As part of a program towards the synthesis of Stemona alkaloids, a novel palladium(II)‐catalyzed C H activation strategy for the construction of such systems has been developed. Starting from simple 1,3‐dienyl‐substituted heterocycles, a large range of polycyclic systems containing pyrrole, indole, furan and thiophene moieties can be synthesized in a single step. 相似文献