Engineering 2D spin networks by on-surface encapsulation of azafullerene radicals in nanotemplates.

We present an efficient strategy for on-surface engineering of organic metal-free supramolecular complexes with long-term spin protection. By vacuum deposition of azafullerene (CN) monomers on a pre-deposited template layer of [10]cycloparaphenylene ([10]CPP) nanohoops on Au(111) surface we exploit the molecular shape matching between the CN and [10]CPP for the azafullerene encapsulation with nanohoops in a guest-host complexation geometry. CN⊂[10]CPP supramolecular complexes self-assemble into an extended two-dimensional hexagonal lattice yielding a high density network of stable spin-1/2 radicals.

Balancing Attraction and Repulsion: The Influence of London Dispersion in [10]Cycloparaphenylene-Fullerene Complexes.

Herein we present a systematic study of the influence of different alkyl chains in malonyl ester fullerene adducts with [10]cycloparaphenylene ([10]CPP]) and a tert-butyl (tBu) ester-substituted [10]CPP analogue. The association constants between the nanoring hosts and the fullerene guests were determined by fluorescence quenching experiments. The trends in association were rationalized by an interplay of repulsion arising from an extended volume and London dispersion as an attractive counterpart.

Cycloparaphenylenes [2+2+2] cycloaddition.

The [2+2+2] cycloaddition (CA) offers great potential as an atom economic method for the formation of substituted aromatic rings. In this article, we highlight the application of this versatile method in synthetic approaches towards substituted cycloparaphenylenes (CPPs). The [2+2+2] CA can take over different tasks within the synthesis depending on the targeted CPP.

Robust coherent spin centers from stable azafullerene radicals entrapped in cycloparaphenylene rings.

Molecular entities with robust spin-1/2 are natural two-level quantum systems for realizing qubits and are key ingredients of emerging quantum technologies such as quantum computing. Here we show that robust and abundant spin-1/2 species can be created in the solid state from spin-active azafullerene CN cages supramolecularly hosted in crystals of [10]cycloparaphenylene ([10]CPP) nanohoops. This is achieved a two-stage thermally-assisted homolysis of the parent diamagnetic [10]CPP⊃(CN)⊂[10]CPP supramolecular complex.

Directed C-H Bond Oxidation of Bridged Cycloalkanes Catalyzed by Palladium(II) Acetate.

We have developed a synthesis of 1,2-substituted adamantane carboxylic acids and further bridged cycloalkanes (cage compounds) by palladium acetate-catalyzed C-H bond oxidation. Acetoxylation of cycloalkane framework was performed using picolylamide as a directing group. Modification of the substrate, ligand design and variation of reaction conditions enabled us to study the mechanism of acetoxylation of aliphatic compounds.