Inserting Nitrogen: An Effective Concept To Create Nonplanar and Stimuli-Responsive Perylene Bisimide Analogues

Abstract

Establishing design principles to create nonplanar π-conjugated molecules is crucial for the development of novel functional materials. Herein, we describe the synthesis and properties of dinaphtho­[1,8-bc:1′,8′-ef]­azepine bisimides (DNABIs). Their molecular design is conceptually based on the insertion of a nitrogen atom into a perylene bisimide core. We have synthesized several DNABI derivatives with a hydrogen atom, a primary alkyl group, or an aryl group on the central nitrogen atom. These DNABIs exhibit nonplanar conformations, flexible structural changes, and ambipolar redox activity. The steric effect around the central nitrogen atom substantially affects the overall structures and results in two different conformations: a nonsymmetric bent conformation and a symmetric twisted conformation, accompanied by a drastic change in electronic properties. Notably, the nonsymmetric DNABI undergoes unique structural changes in response to the application of an external electric field, which is due to molecular motions that are accompanied by an orientational fluctuation of the dipole moment. Furthermore, the addition of a chiral Brønsted base to N-unsubstituted DNABI affords control over the helical chirality via hydrogen-bonding interactions.

Non‐Planar Perylene Bisimide Analogues with Inserted Carbonyl and Methylene Subunits

“…Our group has recently shown that inserting heteroatom(s) into a planar perylene bisimide (PBI) core is a promising approach to design non‐planar π‐systems with unique stimulus‐responsiveness (Figure 1). [7–9] For example, dinaphthoazepine bisimide (DNABI) 1 , a nitrogen‐inserted PBI derivative, underwent structural changes in response to the application of an external electric field, as the molecular motion of the asymmetric acceptor‐donor‐acceptor structure is associated with an orientational change of its dipole moment [7] . Dinaphthothiepine bisimide (DNTBI) S ‐oxide 2 underwent a sulfur‐extrusion reaction upon heating, which enabled the fabrication of an n‐type organic field‐effect transistor by a solution process [8] …”

Acridino[2,1,9,8‐klmna]acridine Bisimides: An Electron‐Deficient π‐System for Robust Radical Anions and n‐Type Organic Semiconductors

“…[29,30] Our group has recently become interested in the development of functional p-conjugated molecules by connecting naphthalene monoimide subunits with heteroatoms. [33][34][35] Herein, we report the synthesis and properties of acridino [2,1,9,8-klmna]acridine bisimides (AABIs) 5a-d (Figure 2b). AABI is an itrogen-doped anthanthrene derivative with two imide substituents.The structure of anthanthrene ( 6) is shown in Figure 2b.A cridino[2,1,9,8-klmna]acridine (7)i s ac lassical nitrogen-doped PA H, but its derivatization has been limited.…”

Mixing Polyaromatic Scaffolds and Main Group Elements: Synthesis, Coordination and Optical Properties of Naphthyl‐Fused Heteropines

“…In this context, the synthesis of heteropines (7‐membered heterocycles featuring heteroelement) recently appeared as an appealing strategy [4] . For example various naphthyl‐fused heteropine incorporating oxygen A , [5] boron B , [6] nitrogen C [7] or phosphorus D [8] have been described in the last years (Scheme 1). All these π‐extended heteropines display a strongly distorted C‐framework and can be emissive in solution.…”