Mechanical Bond-Protected Air-Stable Radicals
Junling Sun, Zhichang Liu, Wei-Guang Liu, Yilei Wu, Yuping Wang, Jonathan C. Barnes, Keith R. Hermann, William A. Goddard III, Michael R. Wasielewski, J. Fraser Stoddart
Abstract
Radical templation centered around a heterotrisradical tricationic inclusion complex DB^(•+)⊂DAPQT^(2(•+)), assembled from an equimolar mixture of a disubstituted 4,4′-bipyridinium radical cation (DB^(•+)) and an asymmetric cyclophane bisradical dication (DAPQT^(2(•+))), affords a symmetric [2]catenane (SC·7PF_6) and an asymmetric [2]catenane (AC·7PF_6) on reaction of the 1:1 complex with diazapyrene and bipyridine, respectively. Both these highly charged [2]catenanes have been isolated as air-stable monoradicals and characterized by EPR spectroscopy. X-ray crystallography suggests that the unpaired electrons are delocalized in each case across two inner 4,4′-bipyridinium (BIPY^(2+)) units forming a mixed-valence (BIPY_2)^(•3+) state inside both [2]catenanes, an observation which is in good agreement with spin-density calculations using density functional theory. Electrochemical studies indicate that by replacing the BIPY^(2+) units in homo[2]catenane HC^(•7+)—composed of two mechanically interlocked cyclobis(paraquat-p-phenylene) rings—with "zero", one, and two more highly conjugated diazapyrenium dication (DAP^(2+)) units, respectively, a consecutive series of five, six, and seven redox states can be accessed in the resulting SC·7PF_6 (0, 4+, 6+, 7+, and 8+), HC·7PF_6 (0, 2+, 4+, 6+, 7+, and 8+), and AC·7PF_6 (0, 1+, 2+, 4+, 6+, 7+, and 8+), respectively. These unique [2]catenanes present a promising prototype for the fabrication of high-density data memories.
Group Members
Sun, J., Liu, Z., Liu, W., Wu, Y., Wang, Y., Barnes, J. C., Hermann, K. R., III, W. A. G., Wasielewski, M. R., & Stoddart, J. F. (2017). Mechanical Bond-Protected Air-Stable Radicals. *J. Am. Chem. Soc.*, *139*(36), 12704-12709. https://doi.org/10.1021/jacs.7b06857