Double Concave Cesium Encapsulation by Two Charged Sumanenyl Bowls.
The controlled reaction of Na and Cs, two alkali metals of different ionic sizes and binding abilities, with sumanene (C21H12) affords a novel type of organometallic sandwich [Cs(C21H11-)2]-, which crystallized as a solvent-separated ion pair with a [Na(18-crown-6)(THF)2]+cation (where THF=tetrahydrofuran). The unprecedented double concave encapsulation of a metal ion by two bowl-shaped sumanenyl anions in [Cs(C21H11-)2]-was revealed crystallographically. Evaluation of bonding and energetics of the remarkable product was accomplished computationally (B2PLYP-D/TZVP/ZORA), providing insights into its formation.
Department of Chemistry, University at Albany, State University of New York, 1400 Washington Avenue, Albany, NY, 12222, USA.
Sarah N
SN
Spisak
Department of Chemistry, University at Albany, State University of New York, 1400 Washington Avenue, Albany, NY, 12222, USA.
Zheng
Z
Wei
Department of Chemistry, Illinois Institute of Technology, Chicago, IL, 60616, USA.
Andrey Yu
AY
Rogachev
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Yamada-oka, Suita, Osaka, 565-0871, Japan.
Toru
T
Amaya
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Yamada-oka, Suita, Osaka, 565-0871, Japan.|The Institute of Scientific and Industrial Research, Osaka University, Mihoga-oka, Ibaraki, Osaka, 567-0047, Japan.
Toshikazu
T
Hirao
Department of Chemistry, University at Albany, State University of New York, 1400 Washington Avenue, Albany, NY, 12222, USA.
Marina A
0000-0003-0221-7900
MA
Petrukhina
alkali metals; concave binding; sandwich products; sumanene; supramolecular assembly