Electron Sharing and Anion–π Recognition in Molecular Triangular Prisms

Abstract

Stacking on a full belly: Triangular molecular prisms display electron sharing among their triangularly arranged naphthalenediimide (NDI) redox centers. Their electron-deficient cavities encapsulate linear triiodide anions, leading to the formation of supramolecular helices in the solid state. Chirality transfer is observed from the six chiral centers of the filled prisms to the single-handed helices.

Functional molecules and materials by π‐Interaction based quantum theoretical design

“…[83] and [88], with permission from Nature Publishing Group and American Chemical Society, respectively). Schneebeli et al [95] designed and synthesized singly right/ left handed self-assemble helices of chiral triangular NDI-D redox prisms (macrocycle composed of linking three electrondeficient naphthalene diimides together using 1,2-diaminocyclohexane) with I 2 3 anion by using cooperative effects of space orbital interaction, p-p/anion-p interactions and electron transfer effects. Watanabe et al [96] designed novel approach for preparing luminescence helically p-stacked assembly of cationic chiral poly(para-phenylene) derivatives by using cooperative intermolecular electrostatic and p-p interactions.…”

Anion–π catalysis: bicyclic products with four contiguous stereogenic centers from otherwise elusive diastereospecific domino reactions on π-acidic surfaces

“…Contributions of anion–π interactions 1,2 to catalysis were first demonstrated explicitly in 2013. 3 Since then, anion–π catalysis has been explored with enolate, 4,5 enamine, 6 iminium, 7 transamination 8 and oxocarbenium 9 chemistry, and the first anion–π enzyme has been created.…”

“…Anion–π catalyst 4 has been designed around the π-acidic surface of a naphthalenediimide (NDI). 2 NDIs offer a privileged platform in anion–π catalysis because their intrinsic quadrupole moment perpendicular to the π surface is very high and can be easily modulated with substituents in the core. 2–8 In anion–π catalyst 4 , this π surface was connected to a tertiary amine catalyst via a fixed Leonard turn.…”

Discovery of the K4 Structure Formed by a Triangular π Radical Anion

“…5 This molecule exhibits reversible six-step reductions on the CV curves due to the strong acceptor ability of the NDI moiety. Although there was no intermolecular π overlap in the crystal structures of neutral NDI-Δ, 5,6 the anionic radical species of NDI-Δ would exhibit three-way branched intermolecular π overlaps due to the exchange interactions ( Figure 2).…”