Functional Corannulene: Diverse Structures, Enhanced Charge Transport, and Tunable Optoelectronic Properties

Abstract

Chemical functionalization of various hydrocarbons, such as coronene, corannulene, and so forth, shows good promise in electronics applications because of their tunable optoelectronic properties. By using quantum chemical calculations, we have investigated the changes in the corannulene buckybowl structure, which greatly affect its electronic and optical properties when functionalized with different electron-withdrawing imide groups. We find that the chemical nature and position of functional groups strongly regulate the stacking geometry, π-stacking interactions, and electronic structure. Herein, a range of optoelectronic properties and structure-property relationships of various imide-functionalized corannulenes are explored and rationalized in detail. In terms of carrier mobility, we find that the functionalization strongly affects the reorganization energy of corannulene, while the enhanced stacking improves hopping integrals, favoring the carrier mobility of crystals of pentafluorophenylcorannulene-5-monoimide. The study shows a host of emerging optoelectronic properties and enhancements in the charge-transport characteristics of functionalized corannulene, which may find possible semiconductor and electronics applications.

Electronic transport properties of selected carbon π-bowls with different size, curvature and solid state packing

“…Due to the complexity and size of organic molecular crystals, most theoretical studies up to date have only addressed the energetics of the interaction between isolated molecular bowls with various metal cations [23][24][25][26][27][28] or the energetics of small assemblies such as corannulene dimers [29][30][31][32] or p-bowl-fullerene binary systems [33][34][35]. Only recently, several studies have explored the optical and vibrational properties of corannulene-based crystals [14,16,36,37]. To the best of our knowledge, no theoretical insights into the electronic transport properties of crystalline bowl-shaped polyarenes have yet been provided.…”

How the substituents in corannulene and sumanene derivatives alter their molecular assemblings and charge transport properties?-A theoretical study with a dimer model

“…As we known, DFT‐D methods are adding an empirical term for the dispersion to correct the deficiencies of DFT functionals in describing the interaction energy. Thus, the total interaction energy was decomposed by two contributions according to a simple method: the pure ωB97X interaction energy and the empirical dispersion contribution . The dispersion interactions (Edis) were calculated by using the BSSE‐corrected binding energy differences.…”

“…Thus, the total interaction energy was decomposed by two contributions according to a simple method: the pure xB97X interaction energy and the empirical dispersion contribution. [25,34] The dispersion interactions (Edis) were calculated by using the BSSE-corrected binding energy differences. As shown in Figure 7, it is obvious that the trends of interaction energy and the dispersion contribution with the substituents are quite similar, but the dispersion contribution is large enough for enhancing the binding stability (i.e., absolute value of interaction energy).…”

“…Lentz et al have compared the difference of corannulene and sumanene from the electron density point of view based on the analysis of Electron Localizability Indicator calculations . Recently, some studies have reported that the solid‐state assemblies can be tailored to form highly ordered stacking when the electron‐withdrawing substituents attached to corannulene, which also exhibited high charge carrier mobility as sumanene . Moreover, many functionalized corannulenes and sumanenes were synthesized and crystallized to show highly regular and densely packed structure with concave‐convex π…π interaction .…”

“…[22] Recently, some studies have reported that the solid-state assemblies can be tailored to form highly ordered stacking when the electronwithdrawing substituents attached to corannulene, which also exhibited high charge carrier mobility as sumanene. [18,[23][24][25] Moreover, many functionalized corannulenes and sumanenes were synthesized and crystallized to show highly regular and densely packed structure with concave-convex p. . .p interac-tion.…”