Investigation of Cycloparaphenylenes (CPPs) and their Noncovalent Ring-in-Ring and Fullerene-in-Ring Complexes by (Matrix-Assisted) Laser Desorption/Ionization and Density Functional Theory.

Abstract

[n]Cycloparaphenylenes ([n]CPPs) with n=5, 8, 10 and 12 and their noncovalent ring‐in‐ring and [m]fullerene‐in‐ring complexes with m=60, 70 and 84 have been studied by direct and matrix‐assisted laser desorption ionization ((MA)LDI) and density‐functional theory (DFT). LDI is introduced as a straightforward approach for the sensitive analysis of CPPs, free from unwanted decomposition and without the need of a matrix. The ring‐in‐ring system of [[10]CPP⊃[5]CPP]+. was studied in positive‐ion MALDI. Fragmentation and DFT indicate that the positive charge is exclusively located on the inner ring, while in [[10]CPP⊃C60]+. it is located solely on the outer nanohoop. Positive‐ion MALDI is introduced as a new sensitive method for analysis of CPP⊃fullerene complexes, enabling the detection of novel complexes [[12]CPP⊃C60, 70 and 84]+. and [[10]CPP⊃C84]+.. Selective binding can be observed when mixing one fullerene with two CPPs or vice versa, reflecting ideal size requirements for efficient complex formation. Geometries, binding and fragmentation energies of CPP⊃fullerene complexes from DFT calculations explain the observed fragmentation behavior.