Study Findings on Alkali Metals Are Outlined in Reports from State University of New York (Record Alkali Metal Intercalation by Highly Charged Corannulene)
By a News Reporter-Staff News Editor at Nanotechnology Weekly -- Current study results on Alkali Metals have been published. According to news reporting out of Albany, New York, by VerticalNews editors, research stated, "The need for advanced energy storage technologies demands the development of new functional materials. Novel carbon-rich and carbon-based materials of different structural topologies attract significant attention in this regard."
Financial support for this research came from Division of Chemistry.
Our news journalists obtained a quote from the research from the State University of New York, "Attractive systems include a unique class of bowl shaped polycyclic aromatic hydrocarbons that map onto fullerene surfaces and are thus often referred to as fullerene fragments, buckybowls, or pi-bowls. Importantly, carbon bowls are able to acquire multiple electrons in stepwise reduction reactions producing sets of successively reduced carbanions. The resulting negatively charged pi-bowls exhibit unique supramolecular assembly and metal intercalation patterns that only recently have begun to be uncovered. First, we have resolved the long-standing mystery behind the supramolecular structure formed by a highly reduced fullerene fragment called corannulene (C20H104-) with multiple lithium ions, using X-ray crystallography coupled with NMR spectroscopy and theoretical calculations. This work provided a new paradigm for lithium ion intercalation between the curved carbon g-surfaces and facilitated understanding of the lithium ion storage mechanism in carbonaceous matrices. Next, we have initiated a new research direction, an investigation of the mixed alkali metal reduction reactions using bowl-shaped corannulene as a remarkable multielectron reservoir and unique ligand with open convex and concave pi-surfaces. As a result, we have revealed the cooperative effect of lithium with heavier Group 1 metals in reduction and self-assembly processes of corannulene. Moreover, we have discovered a new class of organometallic supramolecules having heterometallic cores with high nuclearity and charge such as Li3M36+ and LiM56+ (M = K, Rb, and Cs) sandwiched between two tetrareduced corannulene decks. The resulting triple-decker supramolecular assemblies, fully characterized by X-ray diffraction and spectroscopic methods, were found to exhibit a record ability of the highly charged corannulene pi-surfaces to be fully engaged in intercalation of multiple metal ions. Based on this unique ability, curved pi-ligands with extended carbon frameworks are expected to show remarkable potential for alkali metal storage compared to flat polycyclic arenes. Notably, a previously unseen mode of internal lithium binding revealed in the heterobimetallic sandwiches is accompanied by unprecedented negative shifts (up to -25 ppm) in Li-7 NMR spectra. Based on in-depth analysis of NMR data, augmented by DFT calculations, we have rationalized the observed experimental trends and proposed the mechanism of stepwise alkali metal substitution reactions. Furthermore, we have correlated the origin of the record Li-7 NMR shifts with unique electronic structures of these novel supramolecular aggregates. Herein we present comprehensive analysis of unusual structural and electronic features of remarkable heterometallic self assemblies formed by tetrareduced corannulene, using a wealth of our recent experimental and computational results."
According to the news editors, the research concluded: "This work uncovers unique potential of highly negatively charged bowl-shaped pi-ligands for new supramolecular chemistry and materials chemistry applications."
For more information on this research see: Record Alkali Metal Intercalation by Highly Charged Corannulene. Accounts of Chemical Research, 2018;51(6):1541-1549. Accounts of Chemical Research can be contacted at: Amer Chemical Soc, 1155 16TH St, NW, Washington, DC 20036, USA. (American Chemical Society - www.acs.org; Accounts of Chemical Research - www.pubs.acs.org/journal/achre4)
Our news journalists report that additional information may be obtained by contacting A.V. Zabula, SUNY Albany, Dept. of Chem, Albany, NY 12222, United States. Additional authors for this research include S.N. Spisak, A.S. Filatov, A.Y. Rogachev and M.A. Petrukhina.
The direct object identifier (DOI) for that additional information is: https://doi.org/10.1021/acs.accounts.8b00141. This DOI is a link to an online electronic document that is either free or for purchase, and can be your direct source for a journal article and its citation.
Keywords for this news article include: Albany, New York, United States, North and Central America, Emerging Technologies, Nanotechnology, Supramolecular, Alkali Metals, Fullerenes, Chemistry, State University of New York.
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