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161.
Functionalization of a Ruthenium–Diacetylide Organometallic Complex as a Next‐Generation Push–Pull Chromophore
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Samuel De Sousa Dr. Laurent Ducasse Dr. Brice Kauffmann Prof. Thierry Toupance Dr. Céline Olivier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(23):7017-7024
The design and preparation of an asymmetric ruthenium–diacetylide organometallic complex was successfully achieved to provide an original donor–π–[M]–π–acceptor architecture, in which [M] corresponds to the [Ru(dppe)2] (dppe: bisdiphenylphosphinoethane) metal fragment. The charge‐transfer processes occurring upon photoexcitation of the push–pull metal–dialkynyl σ complex were investigated by combining experimental and theoretical data. The novel push–pull complex, appropriately end capped with an anchoring carboxylic acid function, was further adsorbed onto a semiconducting metal oxide porous thin film to serve as a photosensitizer in hybrid solar cells. The resulting photoactive material, when embedded in dye‐sensitized solar cell devices, showed a good spectral response with a broad incident photon‐to‐current conversion efficiency profile and a power conversion efficiency that reached 7.3 %. Thus, this material paves the way to a new generation of organometallic chromophores for photovoltaic applications. 相似文献
162.
Dr. José I. Urgel Dr. Marco Di Giovannantonio Kristjan Eimre Thorsten G. Lohr Dr. Junzhi Liu Shantanu Mishra Dr. Qiang Sun Amogh Kinikar Dr. Roland Widmer Samuel Stolz Max Bommert Dr. Reinhard Berger Dr. Pascal Ruffieux Dr. Carlo A. Pignedoli Prof. Dr. Klaus Müllen Prof. Dr. Xinliang Feng Prof. Dr. Roman Fasel 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13383-13389
Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on-surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well-controlled ultrahigh-vacuum conditions. Here we report the on-surface synthesis of a polymer linked by cumulene-like bonds on a Au(111) surface via sequential thermally activated dehalogenative C−C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene-like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X-ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on-surface synthesis of cumulene-containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces. 相似文献
163.
Dr. Samuel Stolz Dr. Aliaksandr V. Yakutovich Dr. Jan Prinz Dr. Thomas Dienel Dr. Carlo A. Pignedoli Prof. Dr. Harald Brune Dr. Oliver Gröning Dr. Roland Widmer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18336-18340
Enantioselectivity in heterogeneous catalysis strongly depends on the chirality transfer between catalyst surface and all reactants, intermediates, and the product along the reaction pathway. Herein we report the first enantioselective on-surface synthesis of molecular structures from an initial racemic mixture and without the need of enantiopure modifier molecules. The reaction consists of a trimerization via an unidentified bonding motif of prochiral 9-ethynylphenanthrene (9-EP) upon annealing to 500 K on the chiral Pd3-terminated PdGa{111} surfaces into essentially enantiopure, homochiral 9-EP propellers. The observed behavior strongly contrasts the reaction of 9-EP on the chiral Pd1-terminated PdGa{111} surfaces, where 9-EP monomers that are in nearly enantiopure configuration, dimerize without enantiomeric excess. Our findings demonstrate strong chiral recognition and a significant ensemble effect in the PdGa system, hence highlighting the huge potential of chiral intermetallic compounds for enantioselective synthesis and underlining the importance to control the catalytically active sites at the atomic level. 相似文献
164.
Evan Walter Clark Spotte-Smith Peiyuan Yu Samuel M. Blau Ravi S. Prasher Anubhav Jain 《Journal of computational chemistry》2020,41(24):2137-2150
Thermal storage and transfer fluids have important applications in industrial, transportation, and domestic settings. Current thermal fluids have relatively low specific heats, often significantly below that of water. However, by introducing a thermochemical reaction to a base fluid, it is possible to enhance the fluid's thermal properties. In this work, density functional theory (DFT) is used to screen Diels–Alder reactions for use in aqueous thermal fluids. From an initial set of 52 reactions, four are identified with moderate aqueous solubility and predicted turning temperature near the liquid region of water. These reactions are selectively modified through 60 total functional group substitutions to produce novel reactions with improved solubility and thermal properties. Among the reactions generated by functional group substitution, seven have promising predicted thermal properties, significantly improving specific heat (by as much as 30.5%) and energy storage density (by as much as 4.9%) compared to pure water. 相似文献
165.
James A. Phillips Anna R. Ley Patrick W. Treacy Benjamin M. Wahl Brittany C. Zehner Kelling J. Donald Samuel Gillespie 《International journal of quantum chemistry》2020,120(20):e26383
We have explored the structural and energetic properties of a series of RMX3-NH3 (M=Si, Ge; X=F, Cl; R=CH3, C6H5) complexes using density functional theory and low-temperature infrared spectroscopy. In the minimum-energy structures, the NH3 binds axially to the metal, opposite a halogen, while the organic group resides in an equatorial site. Remarkably, the primary mode of interaction in several of these systems seems to be hydrogen bonding (C-H--N) rather than a tetrel (N→M) interaction. This is particularly clear for the RMCl3-NH3 complexes, and analyses of the charge distributions of the acid fragment corroborate this assessment. We also identified a set of metastable geometries in which the ammonia binds opposite the organic substituent in an axial orientation. Acid fragment charge analyses also provide a clear rationale as to why these configurations are less stable than the minimum-energy structures. Matrix-isolation infrared spectra provide clear evidence for the occurrence of the minimum-energy form of CH3SiCl3–NH3, but analogous results for CH3GeCl3–NH3 are less conclusive. Computational scans of the M-N distance potentials for CH3SiCl3–NH3 and CH3GeCl3–NH3, both in the gas phase and bulk dielectric media, reveal a great deal of anharmonicity and a propensity for condensed-phase structural change. 相似文献
166.
Dr. Luka Ðorđević Cataldo Valentini Dr. Nicola Demitri Cécile Mézière Magali Allain Prof. Dr. Marc Sallé Dr. Andrea Folli Prof. Dr. Damien Murphy Samuel Mañas-Valero Prof. Dr. Eugenio Coronado Prof. Dr. Davide Bonifazi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(10):4135-4143
Herein we report an efficient synthesis to prepare O-doped nanographenes derived from the π-extension of pyrene. The derivatives are highly fluorescent and feature low oxidation potentials. Using electrooxidation, crystals of cationic mixed-valence (MV) complexes were grown in which the organic salts organize into face-to-face π-stacks, a favorable solid-state arrangement for organic electronics. Variable-temperature electron paramagnetic resonance (EPR) measurements and relaxation studies suggest a strong electron delocalization along the longitudinal axis of the columnar π-stacking architectures. Electric measurements of single crystals of the MV salts show a semiconducting behavior with a remarkably high conductivity at room temperature. These findings support the notion that π-extension of heteroatom-doped polycyclic aromatic hydrocarbons is an attractive approach to fabricate nanographenes with a broad spectrum of semiconducting properties and high charge mobilities. 相似文献
167.
Adedamola S. Arojojoye R. Tyler Mertens Samuel Ofori Sean R. Parkin Samuel G. Awuah 《Molecules (Basel, Switzerland)》2020,25(23)
Herein is reported the synthesis of two Au(III) complexes bearing the (R,R)-(–)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (R,R-QuinoxP*) or (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (S,S-QuinoxP*) ligands. By reacting two stoichiometric equivalents of HAuCl4.3H2O to one equivalent of the corresponding QuinoxP* ligand, (R,R)-(–)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (1) and (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (2) were formed, respectively, in moderate yields. The structure of (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (2) was further confirmed by X-ray crystallography. The antiproliferative activities of the two compounds were evaluated in a panel of cell lines and exhibited promising results comparable to auranofin and cisplatin with IC50 values between 1.08 and 4.83 µM. It is noteworthy that in comparison to other platinum and ruthenium enantiomeric complexes, the two enantiomers (1 and 2) do not exhibit different cytotoxic effects. The compounds exhibited stability in biologically relevant media over 48 h as well as inert reactivity to excess glutathione at 37 °C. These results demonstrate that the Au(III) atom, stabilized by the QuinoxP* ligand, can provide exciting compounds for novel anticancer drugs. These complexes provide a new scaffold to further develop a robust and diverse library of chiral phosphorus Au(III) complexes. 相似文献
168.
David M. Koshy Shucheng Chen Dong Un Lee Michaela Burke Stevens Ahmed M. Abdellah Samuel M. Dull Gan Chen Dennis Nordlund Alessandro Gallo Christopher Hahn Drew C. Higgins Zhenan Bao Thomas F. Jaramillo 《Angewandte Chemie (International ed. in English)》2020,59(10):4043-4050
Ni,N‐doped carbon catalysts have shown promising catalytic performance for CO2 electroreduction (CO2R) to CO; this activity has often been attributed to the presence of nitrogen‐coordinated, single Ni atom active sites. However, experimentally confirming Ni?N bonding and correlating CO2 reduction (CO2R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile‐derived Ni,N‐doped carbon electrocatalysts (Ni‐PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO2R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X‐ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square‐planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts. 相似文献
169.
Maxime Balestrat Abhijeet Lale Andr Vinícius Andrade Bezerra Vanessa Proust Eranezhuth Wasan Awin Ricardo Antonio Francisco Machado Pierre Carles Ravi Kumar Christel Gervais Samuel Bernard 《Molecules (Basel, Switzerland)》2020,25(22)
The pyrolysis (1000 °C) of a liquid poly(vinylmethyl-co-methyl)silazane modified by tetrakis(dimethylamido)titanium in flowing ammonia, nitrogen and argon followed by the annealing (1000–1800 °C) of as-pyrolyzed ceramic powders have been investigated in detail. We first provide a comprehensive mechanistic study of the polymer-to-ceramic conversion based on TG experiments coupled with in-situ mass spectrometry and ex-situ solid-state NMR and FTIR spectroscopies of both the chemically modified polymer and the pyrolysis intermediates. The pyrolysis leads to X-ray amorphous materials with chemical bonding and ceramic yields controlled by the nature of the atmosphere. Then, the structural evolution of the amorphous network of ammonia-, nitrogen- and argon-treated ceramics has been studied above 1000 °C under nitrogen and argon by X-ray diffraction and electron microscopy. HRTEM images coupled with XRD confirm the formation of nanocomposites after annealing at 1400 °C. Their unique nanostructural feature appears to be the result of both the molecular origin of the materials and the nature of the atmosphere used during pyrolysis. Samples are composed of an amorphous Si-based ceramic matrix in which TiNxCy nanocrystals (x + y = 1) are homogeneously formed “in situ” in the matrix during the process and evolve toward fully crystallized compounds as TiN/Si3N4, TiNxCy (x + y = 1)/SiC and TiC/SiC nanocomposites after annealing to 1800 °C as a function of the atmosphere. 相似文献
170.
Jos I. Urgel Marco Di Giovannantonio Kristjan Eimre Thorsten G. Lohr Junzhi Liu Shantanu Mishra Qiang Sun Amogh Kinikar Roland Widmer Samuel Stolz Max Bommert Reinhard Berger Pascal Ruffieux Carlo A. Pignedoli Klaus Müllen Xinliang Feng Roman Fasel 《Angewandte Chemie (International ed. in English)》2020,59(32):13281-13287
Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on‐surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well‐controlled ultrahigh‐vacuum conditions. Here we report the on‐surface synthesis of a polymer linked by cumulene‐like bonds on a Au(111) surface via sequential thermally activated dehalogenative C?C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene‐like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X‐ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on‐surface synthesis of cumulene‐containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces. 相似文献