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Dr. Steffen Thies Hanno Sell Dr. Claudia Bornholdt Christian Schütt Dr. Felix Köhler Prof. Dr. Felix Tuczek Prof. Dr. Rainer Herges 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(51):16358-16368
The bistability of spin states (e.g., spin crossover) in bulk materials is well investigated and understood. We recently extended spin‐state switching to isolated molecules at room temperature (light‐driven coordination‐induced spin‐state switching, or LD‐CISSS). Whereas bistability and hysteresis in conventional spin‐crossover materials are caused by cooperative effects in the crystal lattice, spin switching in LD‐CISSS is achieved by reversibly changing the coordination number of a metal complex by means of a photochromic ligand that binds in one configuration but dissociates in the other form. We present mathematical proof that the maximum efficiency in property switching by such a photodissociable ligand (PDL) is only dependent on the ratio of the association constants of both configurations. Rational design by using DFT calculations was applied to develop a photoswitchable ligand with a high switching efficiency. The starting point was a nickel–porphyrin as the transition‐metal complex and 3‐phenylazopyridine as the photodissociable ligand. Calculations and experiments were performed in two iterative steps to find a substitution pattern at the phenylazopyridine ligand that provided optimum performance. Following this strategy, we synthesized an improved photodissociable ligand that binds to the Ni–porphyrin with an association constant that is 5.36 times higher in its trans form than in the cis form. The switching efficiency between the diamagnetic and paramagnetic state is efficient as well (72 % paramagnetic Ni–porphyrin after irradiation at 365 nm, 32 % paramagnetic species after irradiation at 440 nm). Potential applications arise from the fact that the LD‐CISSS approach for the first time allows reversible switching of the magnetic susceptibility of a homogeneous solution. Photoswitchable contrast agents for magnetic resonance imaging and light‐controlled magnetic levitation are conceivable applications. 相似文献
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Dr. Tarun Kumar Yan Yang Sirine Sghaier Dr. Yassir Zaid Dr. Xavier F. Le Goff Dr. Elodie Rousset Dr. Fabien Massicot Dr. Dominique Harakat Agathe Martinez Dr. Marc Taillefer Prof. Laurent Maron Prof. Jean-Bernard Behr Dr. Florian Jaroschik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(12):4016-4021
The development of new fluorine-containing building blocks and their efficient synthetic access is currently a challenging research field. Herein, the highly regio- and stereoselective addition of a large range of aldehydes onto trifluoromethylated benzofulvenes was achieved using a simple La/I2/DIBAL-Cl system via a selective C−F bond activation process. This versatile methodology provided homodienyl alcohols bearing a terminal CF2-alkene with potential further applications, as shown by the dehydration to the first benzofulvenes carrying a difluorovinyl group. In addition, for certain electron-poor aldehydes, unprecedented ipso substitution of the CF3 group in a diene was observed, which, according to DFT studies, is related to the presence of the large, Lewis-acidic lanthanum metal. 相似文献
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Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage 下载免费PDF全文
Ze‐Kun Yang Dong‐Yu Wang Hiroki Minami Hiroyuki Ogawa Takashi Ozaki Dr. Tatsuo Saito Dr. Kazunori Miyamoto Dr. Chao Wang Prof. Dr. Masanobu Uchiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15693-15699
Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod)2] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh3)2Cl2] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot. 相似文献