Spiro-Buckybowls: Synthesis and Selective Transformations Toward Chiral and Nonlinear Optical Polycycles

Integration of spirocycles with buckybowls is a promising strategy to construct three-dimensional (3D) curved pi-systems and to endow distinctive physicochemical features arising from buckybowls. Herein, a series of carbon-bridged spiro-type heterosumanenes (spiro-HSEs) were synthesized by combining 9,9 '-spirobifluorene and dichalcogenasumanenes (DCSs). It is found that spiro-conjugation plays an important role in the geometric and electronic structures of spiro-HSEs. The bowl depth of DCSs moiety becomes larger in the spiro-HSEs. Owing to the Jahn-Teller (J-T) effect, two DCSs segments of spiro-HSEs have different bowl depths accompanied with the unequal distribution of charge in radical cation state. Taking advantage of the typical reactions of DCSs, selective transformations of spiro-HSEs have been adopted in accordance to the nature of chalcogen atoms (S, Se, Te) to bestow the value-added functionalities. The emissive property is enhanced by converting the thiophene rings of S-doped spiro-HSE into thiophene S,S-dioxides. A chiroptical polycycle could be produced by ring-opening of the edge benzene of Se-doped spiro-HSE. The covalent adduct of Te-doped spiro-HSE with Br2 forms non-centrosymmetric halogen-bonded networks, resulting in the high performance second-order nonlinear optics (NLO). Spiro-buckybowls, spiro-type heterosumanenes (spiro-HSEs), are synthesized by fusing together two dichalcogenasumanenes. Selective transformations of a series of doped spiro-buckybowls: in the S-doped spiro-HSE the thiophene is oxidized and the product shows strong emission; ring-opening of the edge benzenes in the Se-doped spiro-HSE provides a chiral polycycle; the covalent adduct of the Te-doped spiro-HSE with Br2 displays second-harmonic generation. image