Designed site-directed dimerization of the monoanion radicals of a π-bowl in the solid state is reported. Dibenzo[a,g]corannulene (C H ) was selected based on the asymmetry of the charge/spin localization in the C H anion. Controlled one-electron reduction of C H with Cs metal in diglyme resulted in crystallization of a new dimer, [{Cs (diglyme)} (C H -C H ) ] (1), as revealed by single crystal X-ray diffraction study performed in a broad range of temperatures. The C-C bond length between two C H 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 C H radicals confirmed that the trans-isomer found in 1 is energetically favored.
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