Synthesis and Crystal Packing Structures of 2,7-Diazapyrenes with Various Alkyl Groups at 1,3,6,8-Positions

“Manipulation” of Crystal Structure by Methylthiolation Enabling Ultrahigh Mobility in a Pyrene‐Based Molecular Semiconductor

“…[ 21 ] The crystal structure of MT‐pyrene shown in Figure is strikingly different from that of parent pyrene, which is known as the sandwich (or dimeric) herringbone structure, [ 22 ] where a pair of pyrene molecules form a π‐stacking dimer that packs into a herringbone‐like motif (vide infra). In sharp contrast, MT‐pyrene forms π‐stacking structures both in the crystallographic [1 0 0] and [1 1 0] directions, which makes the MT‐pyrene packing a new kind of brickwork structure (Figure 2a), [ 23 ] reminiscent of the crystal structure of TIPS‐pentacene. MT‐pyrene forms a lamella structure along the crystallographic c ‐axis direction (Figure 2b), and, as a result, the crystallographic ab plane parallel to the substrate can act as the semiconducting channel in SC‐FETs (vide infra).…”

Peripherally Arylated 2,8-Diazaperylenes from Anthracene Diimide: Synthesis and Oxidative Annulation

“…Consequently, the efficient synthetic methodologies and peripheral functionalization of pyridine-annulated PAHs are useful to modulate their properties and functions. Recently, we have developed reductive aromatization of naphthalene diimide into 2,7-diazapyrene with four pivaloxy (OPiv) groups, which serves as a platform for the synthesis of a variety of tetraaryl-2,7-diazapyrenes (Scheme a) . The reductive aromatization strategy is not limited to naphthalene diimide and should be applicable to various PAH-annulated diimides.…”

2,7-Diazapyrenes: a brief review on synthetic strategies and application opportunities

“…The nature of the substituents in 2,7-diazapyrenes also modulates both the intermolecular interactions in solution and packing structures in the solid state and, compare to other tetraalkyl/tetramethoxy-substituted 2,7-diazapyrene, tetramethyl-substituted 2,7-diazapyrene was found to possess both stronger excimer emission and high electron mobility than other due to the overlaps of low LUMOs because of less steric hindrances. 46 …”

“…In addition, the authors also synthesized the alkylated 2,7-diazapyrene derivative 25 in presence of RANEY® nickel (Scheme 9). 45 Later, the same group provided another approach to afford DAP derivatives bearing various alkyl substituents at 1,3,6,8 positions 27a-c. 46 Being reminiscent to the method outlined above, the new approach was based on 1,3,6,8-tetramethoxy-2,7diazapyrene 26 as a key intermediate. It was then subject to reductive aromatization, followed by alkylation of the latter through Ni-catalyzed cross-coupling with alkyl Grignard reagents (Scheme 10).…”

“…So far, the most common methods involve reductive aromatization of naphthalene diimides, obtained either from naphthalene-1,4,5,8-tetracarboxylic acid or its anhydride, 37,[39][40][41]69 with the following transition metal (TM)-catalyzed coupling reactions with aryl-boronic acids, 45 Grignard reagents 46 or acetylenes. 47 An alternative approach to nonsubstituted 2,7-diazapyrene involves the reaction 2,3-dihydro-1H-benzo[de]isoquinoline with 1,3,5-triazine in polyphosphoric acid.…”