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 C28H14with Cs metal in diglyme resulted in crystallization of a new dimer, [{Cs+(diglyme)}2(C28H14−C28H14)2−] (
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Site‐Directed Dimerization of Bowl‐Shaped Radical Anions to Form a σ‐Bonded Dibenzocorannulene Dimermore » « less
Abstract 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 in1 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 in1 is energetically favored. -
Site‐Directed Dimerization of Bowl‐Shaped Radical Anions to Form a σ‐Bonded Dibenzocorannulene Dimermore » « less
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 C28H14with 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 in1 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 in1 is energetically favored.
