Although similar to carbon monoxide, the chemistry of homoleptic nitrogen monoxide complexes is fundamentally unexplored compared to their carbonyl analogues. Herein we report the synthesis of the first truly homoleptic transition-metal nitrosyl cation as the salt of the weakly coordinating anions (WCAs) [Al(OR ) ] and [F{Al(OR ) } ] (R =C(CF ) ). These salts are easily accessible in good yields, phase pure, and were fully characterized by IR/Raman, NMR and UV/Vis spectroscopy as well as single-crystal and powder X-ray diffraction. They may serve as unprecedented simple model systems for theoretical and experimental studies of nitrosyl complexes.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1002/anie.201904191 | DOI Listing |
Acc Chem Res
February 2024
Université de Lorraine, CNRS, L2CM, F-54000 Nancy, France.
ConspectusThe harvesting and conversion of solar energy have become a burning issue for our modern societies seeking to move away from the exploitation of fossil fuels. In this context, dye-sensitized solar cells (DSSCs) have proven to be trustworthy alternatives to silicon-based cells with advantages in terms of transparency and efficiency under low illumination conditions. These devices are highly dependent on the ability of the sensitizer that they contain to collect sunlight and transfer an electron to a semiconductor after excitation.
View Article and Find Full Text PDFJ Comput Chem
October 2022
Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas, USA.
The π-complexes of cationic coinage metal ions (Cu(I), Ag(I), Au(I)) provide useful experimental support for understanding fundamental characteristics of bonding and C-NMR patterns of the group 11 triad. Here, we account for the role of relativistic effects on olefin-coinage metal ion interaction for cationic, homoleptic tris-ethylene, and tris-norbornene complexes, [M(η -C H ) ] and [M(η -C H ) ] (M = Cu, Ag, Au), as representative case of studies. The M-(CC) bond strength in the cationic, tris-ethylene complexes is affected sizably for Au and to a lesser extent for Ag and Cu (48.
View Article and Find Full Text PDFInorg Chem
December 2021
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States.
Spin-vibronic coupling leads to spin relaxation in paramagnetic molecules, and an understanding of factors that contribute to this phenomenon is essential for designing next-generation spintronics technology, including single-molecule magnets and spin-based qubits, wherein long-lifetime magnetic ground states are desired. We report spectroscopic and magnetic characterization of the isoelectronic and isostructural series of homoleptic zerovalent transition metal triad M(CNDipp) (M = V, Nb, Ta; CNDipp = 2,6-diisopropylphenyl isocyanide) and show experimentally the significant increase in spin relaxation rate upon going from V to Nb to Ta. Correlated electronic calculations and first principle spin-phonon computations support the role of spin-orbit coupling in modulating spin-phonon relaxation.
View Article and Find Full Text PDFInorg Chem
January 2021
Department of Advanced Materials Chemistry, Korea University, Sejong 30019, Korea.
To evaluate the efficacy of -arylation in the second coordination sphere of octahedral iridium complex, a series of homoleptic -heterocyclic carbene (NHC)-based -type complexes were designed and prepared by introducing various substituents (R = H, Me, Ph, MePh, and diMePh) at the -position of the aryl unit of the orthometalated phenyl group. In solution, an unnoticeable increase of emission quantum yields was observed within the variation of the -substituent of the sterically demanding side-branch, a diMePh- group, showing the radiative quantum yield of (Φ = 1.9%), being higher than that of the unsubstituted carbene-based ) (Φ = 1.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2019
Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Universität Freiburg, Albertstrasse 21, 79104, Freiburg, Germany.
Although similar to carbon monoxide, the chemistry of homoleptic nitrogen monoxide complexes is fundamentally unexplored compared to their carbonyl analogues. Herein we report the synthesis of the first truly homoleptic transition-metal nitrosyl cation as the salt of the weakly coordinating anions (WCAs) [Al(OR ) ] and [F{Al(OR ) } ] (R =C(CF ) ). These salts are easily accessible in good yields, phase pure, and were fully characterized by IR/Raman, NMR and UV/Vis spectroscopy as well as single-crystal and powder X-ray diffraction.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!