Synthesis of π-Extended Thiele’s and Chichibabin’s Hydrocarbons and Effect of the π-Congestion on Conformations and Electronic States

[Image: see text] The biradicaloid of Chichibabin’s hydrocarbon exits in a unique thermal equilibrium between closed-shell singlet and open-shell triplet forms. Conceptually, the incorporation of nonplanar aromatic groups, such as anthraquinodimethane (AQD), in these species could bring about stabilization of the individual singlet and triplet spin biradicaloids by creating a high energy barrier for conformational interconversion between folded (singlet) and twisted (triplet) forms. Moreover, this alteration could introduce the possibility of controlling spin states through conformational changes induced by chemical and physical processes. Herein, we report the preparation of AQD-containing, π-extended Thiele’s (A-TH) and Chichibabin’s (A-CH) hydrocarbons, which have highly π-congested structures resulting from the presence of bulky 9-anthryl units. The π-congestion in these substances leads to steric frustration about carbon–carbon double bonds and creates flexible dynamic motion with a moderate activation barrier between folded singlet and twisted triplet states. These constraints make it possible to isolate the twisted triplet state of A-CH. In addition, simple mechanical grinding of the folded singlet of A-CH produces the twisted triplet.