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1.
Acid/Base‐Triggered Switching of Circularly Polarized Luminescence and Electronic Circular Dichroism in Organic and Organometallic Helicenes 下载免费PDF全文
Nidal Saleh Barry Moore II Monika Srebro Nicolas Vanthuyne Loïc Toupet J. A. Gareth Williams Christian Roussel Kirandeep K. Deol Gilles Muller Jochen Autschbach Jeanne Crassous 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1673-1681
Electronic circular dichroism and circularly polarized luminescence acid/base switching activity has been demonstrated in helicene‐bipyridine proligand 1 a and in its “rollover” cycloplatinated derivative 2 a . Whereas proligand 1 a displays a strong bathochromic shift (>160 nm) of the nonpolarized and circularly polarized luminescence upon protonation, complex 2 a displays slightly stronger emission. This strikingly different behavior between singlet emission in the organic helicene and triplet emission in the organometallic derivative has been rationalized by using quantum‐chemical calculations. The very large bathochromic shift of the emission observed upon protonation of azahelicene‐bipyridine 1 a has been attributed to the decrease in aromaticity (promoting a charge‐transfer‐type transition rather than a π–π* transition) as well as an increase in the HOMO–LUMO character of the transition and stabilization of the LUMO level upon protonation. 相似文献
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Bimetallic Gold(I) Complexes with Ethynyl‐Helicene and Bis‐Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties 下载免费PDF全文
Dr. Mehdi El Sayed Moussa Dr. Hui Chen Zuoyong Wang Dr. Monika Srebro‐Hooper Dr. Nicolas Vanthuyne Dr. Soizic Chevance Prof. Christian Roussel Prof. J. A. Gareth Williams Prof. Jochen Autschbach Prof. Régis Réau Prof. Zheng Duan Dr. Christophe Lescop Dr. Jeanne Crassous 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):6075-6086
Monometallic gold(I)‐alkynyl‐helicene complexes ( 1 a , b ) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence ( 2 a , b ) or absence ( 3 a , b ) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2 , 3 ). The influence of the AuI d10 metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of AuI–AuI interactions in 2 a , b . 相似文献
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Bob Boyd Gareth Brenton Eddie Clayton Jonathan Curtis R. M. Elliott G. A. Errock B. N. Green R. H. Bateman Simon J. Gaskell Iwan Griffiths Zdenek Herman Philip Jonathan Rich Kondrat Mila Laušević Chris Lock Deepak Mathur John F. J. Todd Károly Vékey 《Rapid communications in mass spectrometry : RCM》2016,30(11):1253-1264
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Natalie Hell Peter Beiersdorfer Gregory V. Brown Megan E. Eckart Richard L. Kelley Caroline A. Kilbourne Maurice A. Leutenegger Thomas E. Lockard F. Scott Porter Jörn Wilms 《X射线光谱测定》2020,49(1):218-233
X-ray astronomy and ground-based atomic physics have a long history of fruitful collaboration: Sound understanding of the underlying atomic physics is the key to reliable interpretation of the spectra from celestial sources; conversely, astronomical spectra have been used to benchmark and advance atomic physics. This interplay is about to become even more important as we enter a new era of high-resolution X-ray astrophysics with large effective collection area. Although high-resolution observations with the gratings on the Chandra and XMM-Newton observatories continue to drive new science, upcoming planned and proposed missions will open up new discovery space in the near future that is currently challenging to access: high-resolution spectroscopy on extended sources, in the Fe K band, and on short time scales. This review summarizes open questions in these areas and the design parameters for the Hitomi, XRISM, Athena, and Arcus observatories. The expected high quality of spectra taken with these observatories puts new constraints on the accuracy of atomic reference data required to take full advantage of the diagnostic potential of these spectra. 相似文献
7.
Dongshun Ni Brittany P. Witherspoon Hong Zhang Chen Zhou Prof. K. N. Houk Prof. M. Kevin Brown 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(28):11529-11536
A method for the stereoselective [4+2]-cycloaddition of alkenylboranes and dienes is presented. This transformation was accomplished through the introduction of a new strategy that involves the use of chiral N-protonated alkenyl oxazaborolidines as dieneophiles. The reaction leads to the formation of products that can be readily derivatized to more complex structural motifs through stereospecific transformations of the C−B bond such as oxidation and homologation. Detailed computation evaluation of the reaction has uncovered a surprising role of the counterion on stereoselectivity. 相似文献
8.
Emily K. Corlett Helen Blade Leslie P. Hughes Philip J. Sidebottom David Walker Richard I. Walton Steven P. Brown 《Magnetic resonance in chemistry : MRC》2020,58(11):1026-1035
Single-crystal X-ray diffraction structures of the 5-amino-2-methylpyridinium hydrogen fumarate salt have been solved at 150 and 300 K (CCDC 1952142 and 1952143). A base–acid–base–acid ring is formed through pyridinium-carboxylate and amine-carboxylate hydrogen bonds that hold together chains formed from hydrogen-bonded hydrogen fumarate ions. 1H and 13C chemical shifts as well as 14N shifts that additionally depend on the quadrupolar interaction are determined by experimental magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) and gauge-including projector-augmented wave (GIPAW) calculation. Two-dimensional homonuclear 1H-1H double-quantum (DQ) MAS and heteronuclear 1H-13C and 14N-1H spectra are presented. Only small differences of up to 0.1 and 0.6 ppm for 1H and 13C are observed between GIPAW calculations starting with the two structures solved at 150 and 300 K (after geometry optimisation of atomic positions, but not unit cell parameters). A comparison of GIPAW-calculated 1H chemical shifts for isolated molecules and the full crystal structures is indicative of hydrogen bonding strength. 相似文献
9.
Wang Wang Prof. M. Kevin Brown 《Angewandte Chemie (International ed. in English)》2023,62(32):e202305622
The synthesis of polycyclic compounds is of high interest due to the prevalence of these motifs in drugs and natural products. Herein, we report on the stereoselective construction of 3D bicyclic scaffolds and azetidine derivatives by modulation of N-sulfonylimines to achieve either [4+2]- or [2+2]-cycloaddition reactions. The utility of the method was established by further modulation of the product. Mechanistic studies are also included, which support reaction via Dexter energy transfer. 相似文献
10.
Leendert van Dalsen Rachel E. Brown James A. Rossi-Ashton David J. Procter 《Angewandte Chemie (International ed. in English)》2023,62(29):e202303104
The photoactivation of electron donor-acceptor complexes has emerged as a sustainable, selective and versatile strategy for the generation of radical species. Electron donor-acceptor (EDA) complexation, however, imposes electronic constraints on the donor and acceptor components and this can limit the range of radicals that can be generated using the approach. New EDA complexation strategies exploiting sulfonium salts allow radicals to be generated from native functionality. For example, aryl sulfonium salts, formed by the activation of arenes, can serve as the acceptor components in EDA complexes due to their electron-deficient nature. This “sulfonium tag” approach relaxes the electronic constraints on the parent substrate and dramatically expands the range of radicals that can be generated using EDA complexation. In this review, these new applications of sulfonium salts will be introduced and the areas of chemical space rendered accessible through this innovation will be highlighted. 相似文献