We report af acile and efficient method for the covalent 2D-patterning of monolayer graphene via laser irradiation. We utilized the photo-cleavage of dibenzoylperoxide (DBPO) and optimizedthe subsequent radical additions to non-activated graphene up to that level where controlled covalent 2D-patterning of graphene initiated by spatially resolved laser writing is possible.The covalent 2D-functionalization of graphene,w hich is monitored by scanning Raman microscopy(SRM) is completely reversible.This new concept enables write/read/erase control over the covalent chemical information stored on the graphene surface.

Covalently patterned Janus-functionalized graphene featuring a spatially defined asymmetric bifacial addend binding motif remains a challenging synthetic target. Here, a facile and universal laser writing approach for a one-step covalent Janus patterning of graphene is reported, leading to the formation of up to now elusive graphene architectures, solely consisting of antaratopically functionalized superlattices. The structurally defined covalent functionalization procedure is based on laser-triggered concurrent photolysis of two different photosensitizers situated on both sides of the graphene plane, generating radicals and subsequent addend binding in the laser-irradiated areas only. Careful structure analysis was performed by Raman spectroscopy and Kelvin probe force microscopy. In terms of the advantages of our newly established concept, including a simple/easy-to-operate patterning procedure, arbitrary pattern availability, and a high degree of addend binding, an easy access to tailor-designed Janus-functionalized graphene devices with spatially resolved functional entities can be envisaged.

A new concept for the regioselective synthesis of [3 : 2 : 1] hexakis‐adducts of fullerene C60 was developed. Based on sequential tether‐directed remote functionalizations, chiral [3 : 2] pentakis‐adducts with an incomplete octahedral addition pattern were synthesized via stepwise cyclopropanation of C60 with suitable macrocyclic tri‐ and bifunctional cyclomalonate tethers. The four resulting stereoisomers were isolated using chiral HPLC. The corresponding pairs of enantiomers show mirror image behavior in their CD‐spectra. The pentakis‐adducts served as suitable building blocks for the spatially controlled synthesis of mixed hexakis‐adducts. Implementation of functional group‐bearing monomalonates afforded octahedral [3 : 2 : 1] hexakis‐adducts suitable for the construction of larger molecular and supramolecular fullerene architectures in excellent yield.

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Wirb erichten über eine einfacheu nd effiziente Methode fürd ie kovalente 2D-Musterung von Monolagen-Graphen mittels Laserbestrahlung.W ir nutzten die photolytische Spaltung von Dibenzoylperoxid (DBPO) und optimierten die nachfolgenden radikalischen Additionen an nicht aktiviertem Graphen bis zu einem Grad, bei dem eine kontrollierte kovalente 2D-Musterung von Graphen, durch ortsaufgelçstes Laserschreiben initiiert, mçglich ist. Die kovalente 2D-Funktionalisierung von Graphen, die durch Raster-Raman-Mikroskopie (SRM) analysiert wird, ist vollständig reversibel. Dieses neue Konzept ermçglicht die Schreib-/Lese-/ Lçschkontrolle über die auf der Graphenoberflächeg espeicherte kovalentec hemische Information.