Tetrachlorinated Tetraazaperopyrenes (TAPPs): Highly Fluorescent Dyes and Semiconductors for Air‐Stable Organic n‐Channel Transistors and Complementary Circuits

Abstract

A range of 2,9-perfluoroalkyl-substituted tetraazaperopyrene (TAPP) derivatives (1-5) was synthesised by reacting 4,9-diamino-3,10-perylenequinone diimine (DPDI) with the corresponding carboxylic acid chloride or anhydride in the presence of a base. The reaction of compounds 1-4 with dichloroisocyanuric acid (DIC) in concentrated sulphuric acid resulted in the fourfold substitution of the tetraazaperopyrene core, yielding the 2,9-bisperfluoroalkyl-4,7,11,14-tetrachloro-1,3,8,10-tetraazaperopyrenes 6-9, respectively. The optical and electrochemical data demonstrate the drastic influence of the core substitution on the properties. All compounds are highly luminescent (fluorescence quantum yields of up to Φ=0.8). The LUMO energies of the tetrachlorinated TAPP derivatives (determined by cyclic voltammetry and computed by DFT calulations) were found to be below -4 eV. In the course of this work the performance of TAPP derivatives in organic thin-film transistors (TFTs) was investigated, and their n-channel characteristics with field-effect mobilities of up to 0.14 cm(2) V(-1) s(-1) and an on/off current ratio of >10(6) were confirmed. Long-term stabilities of 3-4 months under ambient conditions of the devices were established. Complementary inverters and ring oscillators with n-channel TFTs based on compound 8 and p-channel TFTs based on dinaphtho-[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) were fabricated on a glass substrate.

Core Halogenation as a Construction Principle in Tuning the Material Properties of Tetraazaperopyrenes

“…The vibration involved in the vibronic transitions is the CN stretching mode located at 1450 cm −1 33. As expected, in the multilayer regime the influence of the metal substrate on the optical gap size is negligible, thus, the values obtained from UV/Vis and HREELS are similar (for TAPP‐Cl : 2.64 eV, UV/VIS in THF;33 2.49±0.06 eV, electronic HREELS). However, no variation of the gap size due to the value of the halogen substituent was observed.…”

“…It has been shown in recent years that organic n‐channel thin‐film transistors fabricated with TAPP derivatives as semiconducting material can be operated under ambient conditions. These devices displayed excellent long‐term stability with field‐effect mobility of up to 0.14 cm 2 V −1 s −1 , which was observed for TAPP‐Cl 33. The core‐brominated TAPP derivative TAPP‐Br was also successfully employed in thin‐film transistors; however, the highest electron mobility found for TAPP‐Br (0.032 cm 2 V −1 s −1 ) was about four times lower than found for the chlorinated derivative 34.…”

“…In recent years we developed the synthesis of 1,3,8,10‐tetraazaperopyrenes (TAPP), a new class of polyheterocyclic aromatics 31. 32 TAPP derivatives have shown promising results as both fluorescence markers and organic semiconductors 33–35. Tetrachlorinated, as well as tetrabrominated, TAPPs were demonstrated to display n‐channel semiconducting behavior.…”

Tetra‐N‐silylated Bis(borylene)tetraaminoperylenes (“DIBOTAPs”): Synthesis, Structures and Photophysics

“…[2] More recently, the groups of Paetzold, Ashe, Piers, and others have provided many fascinating examples of this construction principle. [11] The reduction of DPDI with sodium amalgam led to the aromatic, fourfold amino-substituted perylene derivative 3,4,9,10-tetraaminoperylene (TAP). [7] This functionalized perylene could be further converted to 1,3,8,10-tetraazaperopyrene (TAPP) [8,9] and to a range of derivatives [8,10] (Scheme 1), which have already proven to be interesting materials for applications in organic electronic devices.…”

Low density of gap states and unpinned Fermi level inn-channel organic thin-film transistors

“…Many of these applications will benefit from the integration of p-channel and n-channel TFTs in a complementary circuit design, because complementary circuits have distinct advantages over unipolar circuits in terms of power dissipation, noise immunity, and scalability [2][3][4]. Although both p-channel and n-channel organic TFTs have seen significant improvements over the past decade, even the best organic n-channel TFTs [5][6][7][8][9][10] are still inferior to the best organic p-channel TFTs [11,12].…”