Site‐Directed Dimerization of Bowl‐Shaped Radical Anions to Form a σ‐Bonded Dibenzocorannulene Dimer |
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| Authors: | Dr. Sarah N. Spisak Dr. Alexander V. Zabula Melisa Alkan Dr. Alexander S. Filatov Prof. Dr. Andrey Yu. Rogachev Prof. Dr. Marina A. Petrukhina |
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| Affiliation: | 1. Department of Chemistry, University at Albany, State University of New York, Albany, NY, USA;2. Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA;3. Department of Chemistry, Illinois Institute of Technology, Chicago, IL, USA |
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| Abstract: | Designed site‐directed dimerization of the monoanion radicals of a π‐bowl in the solid state is reported. Dibenzo[a,g]corannulene (C28H14) was selected based on the asymmetry of the charge/spin localization in the C28H14.? anion. Controlled one‐electron reduction of C28H14 with Cs metal in diglyme resulted in crystallization of a new dimer, [{Cs+(diglyme)}2(C28H14?C28H14)2?] ( 1 ), as revealed by single crystal X‐ray diffraction study performed in a broad range of temperatures. The C?C bond length between two C28H14.? bowls (1.560(8) Å) measured at ?143 °C does not significantly change upon heating of the crystal to +67 °C. The single σ‐bond character of the C?C linker is confirmed by calculations. The trans‐disposition of two bowls in 1 is observed with the torsion angles around the central C?C bond of 172.3(5)° and 173.5(5)°. A systematic theoretical evaluation of dimerization pathways of C28H14.? radicals confirmed that the trans‐isomer found in 1 is energetically favored. |
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| Keywords: | corannulene dimerization radicals reduction π -bowls |
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