Fuller-Rylenes: Cross-Dimensional Molecular Carbons

Abstract

Fuller-rylenes is a useful model to tailor the properties of cross-dimensional molecular carbons to define their scope for specific applications. Herein we present a straightforward synthetic strategy to hybridize planar rylene dyes and spherical fullerene into esthetic nanostructures containing features from both subunits via one-pot Pd-catalyzed [3 + 2] or [4 + 2] cyclization reactions. Single-crystal X-ray diffraction analysis revealed conclusively the molecular configurations and distinct self-assembly crystal arrangements resulting from the different extension directions of the planar π-systems on the fullerene ball. Our strategy allowed for easy structural and electronic variations; especially, the lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) orbital profiles of the two fuller-rylenes, namely, Fuller-PMI and Fuller-PDI (where PMI refers to as perylene monoamide, and PDI, perylene diimide) molecules, determined by combining fullerene with perylene, which featured different edge structures.

Fuller-Rylenes: Paving the Way for Promising Acceptors

“…Scheme illustrates the detailed syntheses of armless and bay-decorated fuller-rylenes. As unraveled by our previously reported literature, Fuller-PMI was prepared via peri -fusion by Pd-catalyzed [3 + 2] cyclization between perylene monobromide 2 and pristine C 60 in the presence of Pd­(OAc) 2 as the catalyst, PCy 3 ·HBF 4 as the ligand, and K 2 CO 3 as the base in a good yield of 48%. , Therefore, we adopted a similar synthetic procedure for fuller-rylenes with bay arms ( X-Fuller-PMI ). First, PMI ( 1 ) was brominated with liquid bromine in reflux CHCl 3 to obtain perylene tribromide 3 .…”

“…The hybridization of different acceptors remains a fertile ground awaiting exploration, to fully promote the properties of both components . Very recently, we succeeded to exploit cross-dimensional fuller-rylene hybrids by combining a planar perylene dye with spherical fullerene via Pd-catalyzed cyclization reactions containing characteristics of both subunits . Herein, we present our endeavors to reveal the prospects of employing them as promising acceptors in OPVs.…”

“…37 Very recently, we succeeded to exploit cross-dimensional fuller-rylene hybrids by combining a planar perylene dye with spherical fullerene via Pd-catalyzed cyclization reactions containing characteristics of both subunits. 38 Herein, we present our endeavors to reveal the prospects of employing them as promising acceptors in OPVs. Specifically, our strategy allows the supplements and enhance- ment of absorption in the visible region, much wider structural and electronic variations by installing R 1 groups as well as decorating R 2 on the perylene core at will, and good processability without compromising the superior characteristics of fullerene.…”

Molecular Carbon Imides

“…The edge topologies of rylene imides are important to their chemical and physical properties. Taking PMI with a zigzag periphery and PDI with an armchair bay site as the model compounds, the hybridization of spherical fullerene (C 60 ) and planar rylene dye via one-pot Pd-catalyzed [3+2] or [4+2] cyclization generated cross-dimensional MCIs, namely Fuller-PMI ( 29 ) and Fuller-PDI ( 30 ) in moderate yields . Single-crystal X-ray diffraction analysis revealed concave–convex π–π interactions between the two topological units of adjacent molecules but showed different extensions of the planar π-system on the fullerene sphere, thus resulting in distinct supramolecular self-assembled structures.…”

A perylene five-membered ring diimide for organic semiconductors and π-expanded conjugated molecules

“…[14][15][16][17][18][19] However, the incorporation of five-and/or seven-membered ring conjugated units into PDIs has rarely been explored. 20,21 Wu ¨rthner and coworkers have recently disclosed a new expanded PDI by incorporation of azulene into the peri-position of the PDI, yielding a non-alternant isomer of terrylene diimides with NIRabsorption. 22 It should be noted that azulene is a non-alternant non-benzenoid isomer of naphthalene, showing unusual blue color, a large dipole moment, non-symmetric orbitals, and anti-Kasha absorption.…”