Hybrid Supramolecular Naphthalene Diimide‐thiophene Structures and their Application in Polymer Electronics

Abstract

Solution‐processable molecules based on 1,4,5,8‐naphthalenetetracarboxylic diimide (NTCDI, 1), which constitutes the central unit, have been synthesized with thiophene substituents of varying chain length attached to the naphthalene core. In this paper, the synthetic route to this new class of star‐shaped NTCDI derivatives are given. Cyclovoltammetric, UV spectroscopic, photoelectron spectroscopy, and field effect transistor measurements are performed to characterize the electronic and optical properties of the new materials. The relationship between the donor–acceptor structure and the electronic and optical properties is thus shown in detail. Organic field‐effect transistor devices have been built from this series of molecules and the results clearly describe the transfer from n‐type to an ambipolar character depending on the structural components, i.e., naphthalene, diimide, and thiophene, of the molecules.

Core-substituted naphthalenediimides

“…20 Core-substitution with C-C bonds in 55-74 gives generally weaker spectroscopic shifts. 17,18,31,32 Spectacular exceptions include conjugated systems such as the extended diamine 55, absorbing at 692 nm with HOMO/LUMO levels remaining to the range of normal diamines 17 ( Table 1, entry 28). 18 Moreover, mono-, di-and terthiophene donors in the cNDI core of 72-74 push the absorption to 664 nm ( Table 1, entries 45-47, cNDI-oligothiophene and related polymers 75-82 will be covered in a separate chapter).…”

Rational Design of Ambipolar Organic Semiconductors: Is Core Planarity Central to Ambipolarity in Thiophene–Naphthalene Semiconductors?

“…[15] Ambipolar naphthalene diimide-thiophene semiconductors (NTCDI) were also reported by Krüger et al, although their FET performance was modest. [16] Finally, Jenekhe et al recently disclosed a high-mobility ambipolar copolymer based on naphthalenediimide and bithiophene units functionalized with alkoxy chains, PNIBT. [14] In the search for low-band-gap materials for which both facile electron and hole injection are possible from a single type of electrode, we recently synthesized a family of arylene-thiophene derivatives [17] ( Figure 2).…”

Tuning of the Electronic Levels of Oligothiophene–Naphthalimide Assemblies by Chemical Modification

“…In addition, they have excellent thermal and oxidative stability, high electron affinities, and, in most cases, high electron mobilities . Functionalization of these rylene materials with electron donor groups, such as oligothiophenes, or extension of the π‐conjugated system has allowed ambipolar charge transport …”

“…[11][12][13][14][15][16][17] Functionalization of these rylene materials with electron donor groups,s uch as oligothiophenes, [18][19][20] or extension of the pconjugated system has allowed ambipolar charget ransport. [21][22][23][24][25][26][27][28] In the search for low-bandgap materials in which facile electron and hole injection are both possiblef rom as inglet ype of electrode, [20,21,[29][30][31][32][33][34] we have synthesized and characterized different oligothiophene-naphthalimide assemblies ( Figure 1) in which both donora nd acceptorm oieties are directly conjugated through rigid linkers.…”