Dinaphtho[1,2-b:2′,1′-d]chalcogenophenes: Comprehensive Investigation of the Effect of the Chalcogen Atoms in the Phenacene-Type π-Electronic Cores

Abstract

We report dinaphtho[1,2-b:2′,1′-d]chalcogenophenes as a new class of highly potential p-type semiconductors. As the result of comprehensive investigations including computational studies based on single-crystal structures successfully determined by X-ray analysis, the impacts of the chalcogen atoms are substantially manifested in their molecular orbitals, crystal packing structures, chargetransporting properties, and the device performances at the end. Among them, dinaphtho[1,2-b:2′,1′-d]thiophene and dinaphtho[1,2-b:2′,1′-d]selenophene achieved a hole mobility of up to 1.6 and 2.0 cm 2 V −1 s −1 , respectively, accompanied by an I on /I off ratio as high as 10 4 −10 5 in their single-crystal organic field-effect transistors. Such high performances are attributed to the large orbital coefficient on the chalcogen atoms and the ideal packing structures induced by chalcogen-bridged W-shaped molecules.

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

“…S atom appears to have the right size for herringbone packing motif and favors well‐balanced transfer integrals in conduction planes . A relative superiority of the S atom over the O atom is also observed . The too rapid conclusion of the superiority of S‐containing molecular semiconductors over O and Se analogs must be tempered by the fact that few homologous series have been reported and that crystal structures are sometimes substantially different.…”

Critical analysis of fragment-orbital DFT schemes for the calculation of electronic coupling values

“…43 This approach is very simple to implement in most electronic structure codes and therefore widely used. 26,30,42,[50][51][52] 2.…”

“…Although there are -depending on the exact charge transport mechanism -a number of other parameters influencing the process, electronic couplings often serve as a first descriptor for gauging the charge transfer efficiency, especially in the field of organic electronics. [23][24][25][26] An accurate estimate of H ab is thus of great importance for the theoretical study of electron or hole transfer reactions.…”

Transistor Properties of 2,7-Dialkyl-Substituted Phenanthro[2,1-b:7,8-b′]dithiophene

“…In this paper, we propose a strategic approach to improving the μ value based on a recent study of picene and dinaphtho[1,2- b :2′,1′- d ]chalcogenophenes22. This strategy follows from the fact that the HOMO level’s structure in 2 is different from that in 1, which exhibits very high FET performance.…”