Conjugation-Induced Spin Delocalization in Helical Chiral Carbon Radicals via Through-Bond and Through-Space Effects

A class of highly stable hydrocarbon radicals with helical chirality are synthesized, which can be isolated and purified by routine column chromatography on silica gel. These carbon-centered radicals are stabilized by through-bond delocalization and intramolecular through-space conjugation, which is evidenced by Density Functional Theory (DFT) calculation. The high stability enables to directly modify the carbon radical via palladium-catalyzed cross-coupling with the radical being untapped. The structures and optoelectronic properties are investigated with a variety of experimental methods, including Electron Paramagnetic Resonance (EPR), Ultraviolet Visisble Near Infrared (UV-vis-NIR) measurements, Cyclic Voltammetry (CV), Thermogravimetry Analysis (TGA), Circular Dichroism (CD) spectra, High-Performance Liquid Chromatography (HPLC), and X-ray crystallographic analysis. DFT calculations indicated that the 9-anthryl helical radical is more stable than its tail-to-tail sigma-dimer over 13.2 kJ mol-1, which is consistent with experimental observations. A class of stable carbon radicals that are stabilized by delocalization through both through-bond and through-space conjugation, are successfully synthesized. The resulting helical structure not only makes the radicals inherently chiral, but also provides great stability, making them ideal for both optoelectronic property investigation and direct chemical decoration.image