Magic-Angle Stacking and Strong Intermolecular π–π Interaction in a Perylene Bisimide Crystal: An Approach for Efficient Near-Infrared (NIR) Emission and High Electron Mobility

Abstract

A single crystal of N,N'-bis(4-methoxybenzyl)perylene-3,4,9,10-bis(dicarboximide) (mb-PBI) that possesses novel magic-angle stacking (M-type stacking) and strong intermolecular π-π interaction is achieved by physical vapor transport (PVT), which shows attractive optoelectronic functions such as efficient NIR emission and high electron mobility. In this special M-type staking, the strong Frenkel/CT mixing state promotes fluorescence and, importantly, the elimination of long-distance Förster resonance energy transfer enables the minimization of the possible fluorescence quenching, which ensure the highly efficient emission. Moreover, the strong π-π interaction elongates the "supramolecular conjugation" to reduce the energy gap and also benefits the electron mobility of the crystal. The experimental results clearly indicate that M-type staking is a novel approach to optimize the optoelectronic functions of organic semiconducting materials.

Null Exciton Splitting in Chromophoric Greek Cross (+) Aggregate

“…Molecular aggregates exhibiting minimal exciton interactions can have important implications in photonic devices . Chromophoric “M‐aggregates” possessing magic angle stacking ( θ =54.7°) and “null‐aggregates” have been reported to possess minimal net exciton interaction in the condensed state. Cross‐stacked chromophoric assemblies with near‐orthogonal transition dipoles ( α ≈90°) can also ensue minimal exciton interactions .…”

Crystal Engineering of 1D Exciton Systems Composed of Single‐ and Double‐Stranded Perylene Bisimide J‐Aggregates

“…[ 18–20 ] These insights from small model systems now motivate the engineering of unprecedented PBI packing arrangements in solid‐state materials with the goal to tailor functional properties for applications of these dyes beyond their conventional ones as color pigments. [ 21–25 ] Here of particular interest is the longitudinal slip‐stack arrangement of the dyes that affords dye aggregates with significant bathochromic shifts of the absorption and emission bands and high exciton mobilities originating from J‐type exciton coupling. [ 26 ] Accordingly, the aim of this work was to engineer a slip‐stacked packing arrangement of PBI dyes to afford a new class of PBI pigments with solid‐state properties that are distinguished from the common cofacially stacked color pigment materials.…”

Facile Synthetic Route for Direct Access of Perylenediimide Single Crystals in High Yield through In Situ Crystallization

“…However, single crystal structural analysis of PDIs are expected to provide better understanding of molecular assembly and structure‐property relationship in the bulk materials . Physical vapor transport (PVT) method is the mostly utilized method for growing single crystals of PDIs based materials . However, PVT method is complex and required costly instrument to provide vacuum and/or an inert carrier gas environment .…”