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41.
Fabian Gerson Axel Lamprecht Markus Scholz Heinz Troxler Dieter Lenoir 《Helvetica chimica acta》1996,79(1):307-318
The radical anions of 5H-dibenzo[a,d]cycloheptene ( 9 ), 5 H-dibenzo[c,f][1,2]diazepine ( 10 ), 5,6-dihydrodibenzo[a,e]cyclooctene ( 11 ), 5,6-dihydrodibenzo[c,g][1,2]diazocine ( 12 ), and (E)-2,2,5,5-tetramethyl-3,4-diphenylhex-3-ene ( 13 ) were characterized by ESR and ENDOR spectroscopy. Their hyperfine data were compared with those previously reported for radical anions also containing the stilbene or the azobenzene π-system. Whereas the π-spin distribution in the radical anions of the stilbene series is only moderately sensitive to deviations of the π-system from planarity, the radical anions of the azobenzene series respond to steric strain by shifting the π-spin population from the benzene rings to the azo group. This finding is impressively demonstrated by the similar hyperfine data for 9 · ? and 11 · ? which contrast with the strongly highly hindered 13 · ?. A. plausible interpretation is readily provided by the electron affinities of the constituent π-moieties in stilbene and azobenzene. While those of benzene and ethene are both comparatively low, the azo group has a considerably higher electron affinity. 相似文献
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Jeremy M. Kaminski Angela Rodríguez-Serrano Fabian Dinkelbach Hector Miranda-Salinas Andrew P. Monkman Christel M. Marian 《Chemical science》2022,13(23):7057
Quantum chemical studies employing combined density functional and multireference configuration interaction methods suggest five excited electronic states to be involved in the prompt and delayed fluorescence emission of TpAT-tFFO. Three of them, a pair of singlet and triplet charge transfer (CT) states (S1 and T1) and a locally excited (LE) triplet state (T3), can be associated with the (Me → N) conformer, the other two CT-type states (S2 and T2) form the lowest excited singlet and triplet states of the (Me → Ph) conformer. The two conformers, which differ in essence by the shearing angle of the face-to-face aligned donor and acceptor moieties, are easily interconverted in the electronic ground state whereas the reorganization energy is substantial in the excited singlet state, thus explaining the two experimentally observed time constants of prompt fluorescence emission. Forward and reverse intersystem crossing between the singlet and triplet CT states is mediated by vibronic spin–orbit interactions involving the LE T3 state. Low-frequency vibrational modes altering the distance and alignment of the donor and acceptor π-systems tune the S1 and T3 states (likewise S2 and T3) into and out of resonance. The enhancement of intersystem crossing due to the interplay of vibronic and spin–orbit coupling is considered a general feature of organic through-space charge-transfer thermally activated delayed fluorescence emitters.DFT/MRCI quantum chemical studies suggest five excited electronic states to be involved in the prompt and delayed fluorescence emission of TpAT-tFFO. 相似文献
43.
Fabian Ebner Philipp Mainik Dr. Lutz Greb 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(16):5120-5124
Structural constraint represents an attractive tool to modify p-block element properties without the need for unusual oxidation or valence states. The recently reported methyl-calix[4]pyrrolato aluminate established the effect of forcing a tetrahedral aluminum anion into a square-planar coordination mode. However, the generality of this structural motif and any consequence of ligand modification remained open. Herein, a systematic ligand screening was launched, and the class of square-planar aluminum anions was extended by two derivatives that differ in the meso-substitution at the calix[4]pyrrolato ligand. Strikingly, this modification provoked opposing trends in the preference for a Lewis acidic binding mode with σ-donors versus the aluminum-ligand cooperative binding mode with carbonyls. Insights into the origin of these counterintuitive experimental observations were provided by computation and bond analysis. Importantly, this rationale might allow to exploit mode-selective binding for catalytic rate control. 相似文献
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Fabian Gyger André Sackmann Michael Hübner Pascal Bockstaller Dagmar Gerthsen Henning Lichtenberg Jan‐Dierk Grunwaldt Nicolae Barsan Udo Weimar Claus Feldmann 《Particle & Particle Systems Characterization》2014,31(5):591-596
Pd@SnO2 and SnO2@Pd core@shell nanocomposites are prepared via a microemulsion approach. Both nanocomposites exhibit high‐surface, porous matrices of SnO2 shells (>150 m2 g?1) with very small SnO2 crystallites (<10 nm) and palladium (Pd) nanoparticles (<10 nm) that are uniformly distributed in the porous SnO2 matrix. Although similar by first sight, Pd@SnO2 and SnO2@Pd are significantly different in view of their structure with Pd inside or outside the SnO2 shell and in view of their sensor performance. As SMOX‐based sensors (SMOX: semiconducting metal oxide), both nanocomposites show a very good sensor performance for the detection of CO and H2. Especially, the Pd@SnO2 core@shell nanocomposite is unique and shows a fast response time (τ90 < 30 s) and a very good response at low temperature (<250 °C), especially under humid‐air conditions. Extraordinarily high sensor signals are observed when exposing the Pd@SnO2 nanocomposite to CO in humid air. Under these conditions, even commercial sensors (Figaro TGS 2442, Applied Sensor MLC, E2V MICS 5521) are outperformed. 相似文献
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Inside Back Cover: Multiple and Highly Selective Alkyne–Isonitrile C−C and C−N Couplings at Group 4 Metallocenes (Chem. Eur. J. 27/2016)
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