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Fe to Ru electron transfer is initiated by the inclusion of saturated bridging ligands into the β-cyclodextrin (CD) cavity of [2]rotaxane complexes and is observed as an intervalence charge transfer (IVCT) band in the electronic spectra. The rotaxanes are synthesized by using Ru and Fe complexes as stoppers, β-CD as the cyclic molecular head, and 4,4'-bipyridine derivatives with interrupted π-electron system as the bridging ligand between the metal centers.
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http://dx.doi.org/10.1002/1521-3773(20010119)40:2<446::AID-ANIE446>3.0.CO;2-N | DOI Listing |
Inorg Chem
September 2025
Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States.
We have prepared a series of strongly fluorescent NO-bis (phenolate) aza-dipyrromethene dyes incorporating boron (aza-BODIPY), aluminum (aza-ALDIPY), gallium (aza-GADIPY), and indium (aza-INDIPY). These compounds were oxidized both chemically and electrochemically to give diradical molecules - with an open-shell singlet ground state and a thermally accessible triplet excited state. The ground state behavior of these diradical molecules was confirmed by a wide array of magnetic spectroscopies, including variable-temperature H NMR, EPR, and SQUID.
View Article and Find Full Text PDFNat Commun
August 2025
School of Science, School of Materials Science and Engineering, School of Biomedical Engineering, Harbin Institute of Technology, Shenzhen, Guangdong, 518055, China.
Developing low-energy-gap materials for efficient photothermal conversion provides promising candidates for solar energy utilization. Herein, we explore the feasibility of employing robust organic radical cations as near-unity solar absorbers for practical seawater evaporation. Gram-scale organic radical cations are straightforwardly synthesized through single-electron oxidation.
View Article and Find Full Text PDFDalton Trans
July 2025
University of Vienna, Institute of Inorganic Chemistry, Währinger Strasse 42, 1090 Vienna, Austria.
An organic-inorganic diamine, 1,3-bis(aminopropyl)tetraphenyldisiloxane, was prepared and introduced as a flexible spacer into the structure of a salen-type Schiff base (H2L7) extending the available small library of similar compounds derived from 1,3-bis(aminopropyl)tetramethyldisiloxane and substituted 2-hydroxybenzaldehydes (H2L1-H2L6). Like the previously reported mononuclear copper(II) complexes [CuL1]-[CuL6], the new copper(II) complex [CuL7], obtained by reaction of Cu(OAc)·HO with H2L7 in a mixture of organic solvents, has a tetrahedrally distorted square-planar (NO) coordination geometry. X-ray crystallography has shown that compared to [CuL1]-[CuL6] the Si-O-Si angle in [CuL7] is even closer to linear due to stronger intramolecular interactions between Ph groups than between Me groups in the central-RSi-O-SiR- fragment (R = Ph and Me, respectively).
View Article and Find Full Text PDFChemistry
August 2025
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.
Molecular systems with symmetric resonance structures with invertible polarization (SRIP) have been reported to exhibit negative second hyperpolarizability, which is unusual for ordinal molecular systems. We herein report that mixed-valence systems can also be recognized as SRIP systems showing negative second hyperpolarizability. Since electronic structures of MV systems are often represented by the Robin-Day classification, we theoretically investigated the correlation between the Robin-Day class and second hyperpolarizability γ in simple MV systems such as He and biaryl derivatives.
View Article and Find Full Text PDFChem Sci
June 2025
Department of Chemistry, University of Warwick CV4 7AL Coventry UK
The absorption spectra of a series of Ce-oxo clusters (molecular nanoparticles) with sizes ranging from 3 to 100 Ce atoms per cluster are reported. The O 2p to Ce 4f charge-transfer absorption onset in these systems is unaffected by size and almost identical to that of 5 nm CeO particles and other Ce based materials such as the metal-organic framework Ce-UiO-66. This clearly demonstrates that in CeO based systems, with highly localized 4f LUMO orbitals, quantum confinement effects are not influential on electronic structure.
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