Highly stable and isomorphic donor–acceptor stacking in a family of n-type organic semiconductors of BTBT–TCNQ derivatives

Abstract

Unsymmetrically substituted donor–acceptor type compounds exhibit an isomorphous layered packing structure, which is discussed in terms of DFT-based quantum chemical calculations.

New charge-transfer complexes of 1,2,5-chalcogenadiazoles with tetrathiafulvalenes

“…π-Stacking arrangements and the dominance of dispersion interactions are typical for CT complexes. 110…”

Alkyl-Parity Controlled Switching of Polar/Antipolar Organic Semiconductors

“…We developed and synthesized a series of pTol-BTBT-C n substituted with various alkyl chain lengths (n = 5−14) by a synthetic route reported for pTol-BTBT-C 10 . [32] Full crystal structure analyses for all the compounds were successfully conducted, the results of which are presented in Figures S1−S5 and Table S1. The obtained packing motifs of all the compounds are composed of molecular alignments with long axes parallel to each other, but can be classi ed into three categories, depending on the alkyl chain length, as shown in Figure 1.…”

“…[7,11,12] Meanwhile, alkyl substitutions are effective for obtaining highly layered-crystalline organic semiconductors (OSCs) that are well suited for manufacturing organic eld-effect transistors (OFETs). [19][20][21][22][23][24][25][26][27][28][29][30][31][32] Substitutions of extended fused-ring π-electron skeletons (or π-cores) by relatively long alkyl chains enabled the development of several solution-processable OSCs with layered crystalline structures, which afforded OFETs with excellent carrier transport characteristics. [33][34][35][36][37][38][39][40][41] A notable example is phenyl-/alkylated- [1]benzothieno [3,2-b][1]benzothiophene (Ph-BTBT-C n ), in which the long-axis ends of the BTBT π-core are substituted by phenyl and alkyl groups.…”

“…[43] However, the parity of n does not affect the overall molecular packing structure, despite the clear parity dependence of terminal C-C bond orientation in the crystals. Each unidirectionally-oriented (polar) monomolecular layer is stacked alternately via head-to-head and tail-totail (where the head and tail denote phenyl and alkyl groups, respectively) alignments to form bilayer-type herringbone (b-LHB) packing [28][29][30][31][32] (which is later denoted also as antipolar-type herringbone), although a slight variation in the packing motif with an increase in n was observed in Ph-BTBT-C n . Parity-sensitive and parity-dependent variations in interlayer stacking have not been reported for any alkylated OSCs.…”

Boundary research between organic conductors and transistors: new trends for functional molecular crystals

“…7). 199 The dispersion force is the primary force of attraction between the donor and acceptor and the repulsive short-range (orbit–orbit) interactions play important roles in determining the stacking configuration in the co-crystals. However, it was often claimed that CT interactions could be the main contributors to the attraction in donor–acceptor compounds.…”