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Synthesis, Structure, and Optical Property of Tris(biaryldiyl)metal Complexes Consisting of Group 9 Elements.
Inorg Chem
November 2024
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
We report the synthesis and characterization of tris(biphenyl-2,2'-diyl)metal complexes of trivalent group 9 elements (, M = Co, Rh, Ir) and their nonplanarly π-extended analogs, tris(1,1'-binaphthyl-2,2'-diyl)metal complexes (, M = Rh, Ir). Single crystal X-ray crystallography reveals the distorted octahedral geometry with an approximate symmetry of trianionic complexes (M = Co, Rh, Ir) and (M = Rh, Ir), which are contacted by three Li ions in the crystal. Complex exhibits yellow luminescence in THF with a photoluminescence quantum yield () of up to 0.
View Article and Find Full Text PDFAttosecond formation of charge-transfer-to-solvent states of aqueous ions probed using the core-hole-clock technique.
Nat Commun
October 2024
Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20, Uppsala, Sweden.
Charge transfer between molecules lies at the heart of many chemical processes. Here, we focus on the ultrafast electron dynamics associated with the formation of charge-transfer-to-solvent (CTTS) states following X-ray absorption in aqueous solutions of Na, Mg, and Al ions. To explore the formation of such states in the aqueous phase, liquid-jet photoemission spectroscopy is employed.
View Article and Find Full Text PDFAtomically precise rhodium-indium carbonyl nanoclusters: synthesis, characterization, crystal structure and electron-sponge features.
Nanoscale
October 2024
Department of Industrial Chemistry "Toso Montanari", University of Bologna, Via Gobetti 85, 40129 Bologna, Italy.
In this paper we present the investigation of the reactivity of [Rh(CO)] with InCl, with the aim of expanding the more general study that allowed us to obtain, among other species, the icosahedral [RhE(CO)] ( = 4 when E = Ge or Sn; = 3 when E = Sb or Bi) family of clusters. Indeed, the study resulted in the isolation and characterization of the analogous In-centred icosahedral [RhIn(CO)] nanocluster (1), which is isoelectronic and isostructural with the [RhE(CO)] congeners. During the course of the reaction two more new species, namely the octahedral [Rh(CO)InCl] (2) and the dimeric [{Rh(CO)InCl}] (3) have also been identified.
View Article and Find Full Text PDF-M(CO)(PNP) pincer complexes (M = W(0) or Re(I); PNP = 4,5-bis(diphenylphosphino)acridine): synthesis, spectroscopy and anti-Kasha emission.
Dalton Trans
September 2024
Faculty of Chemistry, VNU University of Science, 19 Le Thanh Tong, Hoan Kiem, Hanoi, Vietnam, 11021.
Two isoelectronic and isostructural W(0) and Re(I) complexes -W(CO)(PNP) (1) and [-Re(CO)(PNP)]Cl (2) (PNP = 4,5-bis(diphenylphosphino)acridine) were synthesized and characterized by X-ray diffraction, infrared, electronic absorption and emission spectroscopy, and cyclic voltammetry. Structures of these complexes show a metal center bonded to the pincer ligand and two axial CO and one equatorial CO ligands. DFT calculations showed that the LUMOs of both complexes are the lowest energy π* orbitals localized in the acridine part of the ligand.
View Article and Find Full Text PDFIntroduction of Niobium in the Chemistry of Octahedral Chalcogenide Clusters: Synthesis and Detailed Study of Compounds Based on Condensed and Discrete {ReNbQ} (Q = S or Se) Cores.
Inorg Chem
August 2024
Nikolaev Institute of Inorganic Chemistry SB RAS, 3, Acad. Lavrentiev ave., Novosibirsk 630090, Russia.
Article Synopsis
- Niobium typically doesn't form cluster chalcogenide compounds like other group 6 and 7 metals, but this study successfully created niobium-containing clusters based on {ReNb(μ-S)} and {ReNb(μ-Se)} cores.
- The synthesis involved high-temperature reactions of rhenium and niobium dichalcogenides in a KCN melt, resulting in 1D polymers that mirror the structure of known heterometallic clusters.
- The new clusters were analyzed for their structure and properties using various techniques, revealing significant electrochemical activity with the ability to undergo reversible redox transitions, and showing a notable trend in redox potentials based on their cluster composition.
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