π‐Extended Pyrrole‐Fused Heteropine: Synthesis, Properties, and Application in Organic Field‐Effect Transistors

Abstract

Sulfur‐embedded polycyclic aromatic compounds have been used as building blocks for numerous organic semiconductors over the past few decades. While the success is based on thiophene‐containing compounds, aromatic compounds that contain thiepine, a sulfur‐containing seven‐membered‐ring arene, has been less well investigated. Here we report the synthesis and properties of π‐extended pyrrole‐fused heteropine compounds such as thiepine and oxepine. A π‐extended pyrrole‐fused thiepine exhibited a “pitched π‐stacking” structure in the crystal, and exhibited a high charge carrier mobility of up to 1.0 cm2 V−1 s−1 in single‐crystal field‐effect transistors.

Synthesis and Properties of Azahomocorannulenyl Cations and Radicals

“… [30,31] In our continuous research, we decided to design and synthesize a ring‐expanded analog of molecule 1 . Herein, we report on the synthesis and properties of azahomocorannulene derivatives 2 , [32–34] in which one of the hexagons in the corannulene core of 1 is substituted by a heptagon ring. With the introduction of the heptagon ring, it acquires a 2‐azaazulene structure [35–37] in its center, which is a non‐alternant structure of 2‐azanaphthalene.…”

1,3‐Dipolar Cycloaddition of Polycyclic Aromatic Azomethine Ylides and Alkynylbenziodoxoles for Synthesis of Functional Dibenzoullazines†

“…In this context, our research group has been actively engaged in the synthesis of functional polycyclic aromatic molecules bearing heteroatoms. [ 20 ] We have developed a novel approach involving the 1,3‐dipolar cycloaddition of polycyclic aromatic azomethine ylides with various dipolarophiles bearing C–C double bonds [ 21‐26 ] and C–C triple bonds, [ 27‐29 ] which effectively yields dibenzoullazine structures. [ 10,18,30‐34 ] As our research progressed, we became intrigued by the potential of alkynyl–iodine(III) reagents as valuable building blocks in organic synthesis.…”

Liquid Crystalline Magneto-Optically Active Peralkylated Azacoronene

“…Pyrrole-fused compounds are molecular scaffolds containing several pyrrole rings that are fused together or annulated with other aromatic or heterocyclic ring systems. These heterocyclic nanographene motifs , offer unique electronic, photophysical, redox, and biological properties and therefore are potential candidates for applications ranging from organic electronics, − sensing, − and even as substructures of potential drug candidates. − Additionally, they often exhibit high thermal stability and are chemically robust. ,,− Azacoronenes, a subclass of pyrrole-fused compounds, are of particular interest for their optical and redox properties. , These molecules are characterized by a structure that consists of a central benzene core substituted by six fused pyrrole rings. The synthesis of unsubstituted hexapyrrolohexaazacoronene ( HPHAC ) (Figure ) was initially attempted by Lazerges et al via the oxidation of hexapyrrolylbenzene with iron­(III) perchlorate; however, only partially oxidized species were observed by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry.…”