Cyclophanes of different ring sizes featuring perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) linked by flexible malonates were designed, synthesized, and investigated with respect to their structural, chemical and photo-physical properties. It is...

We investigate the gas-phase chemistry of noncovalent complexes of [10]cycloparaphenylene ([10]CPP) with C 60 and C 70 by means of atmospheric pressure photoionization and electrospray ionization mass spectrometry. The literature-known [1 : 1] complexes, namely [10]CPP�C 60 and [10]CPP�C 70 , are observed as radical cations and anions. Their stability and charge distribution are studied using energyresolved collision-induced dissociation (ER-CID). These measurements reveal that complexes with a C 70 core exhibit a greater stability and, on the other hand, that the radical cations are more stable than the respective radical anions. Regarding the charge distribution, in anionic complexes charges are exclusively located on C 60 or C 70 , while the charges reside on [10]CPP in the case of cationic complexes.[2 : 1] complexes of the ([10]CPP 2 �C 60/70 ) + */À * type are observed for the first time as isolated solitary gas-phase species.Here, C 60 -based [2 : 1] complexes are less stable than the respective C 70 analogues. By virtue of the high stability of cationic [1 : 1] complexes, [2 : 1] complexes show a strongly reduced stability of the radical cations. DFT analyses of the minimum geometries as well as molecular dynamics calculations support the experimental data. Furthermore, our novel gas-phase [2 : 1] complexes are also found in 1,2-dichlorobenzene. Insights into the thermodynamic parameters of the binding process as well as the species distribution are derived from isothermal titration calorimetry (ITC) measurements.

Two [60]fullerene dumbbell-like molecules with a single or double perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) linker were synthesized to study the structural and photo-physical properties in addition to the complex formation with [10]CPP. Due to their special optical properties, it is possible to describe the complexation using conventional spectroscopic methods such as NMR and fluorescence. However, isothermal titration calorimetry (ITC) completed the analysis of the bis-pseudorotaxane formation by investigating the binding stoichiometries as well as the thermodynamic and kinetic parameters. It was observed that the PBI bridges do not inhibit the complexation with [10]CPP, giving rise to the formation of 1:1 and 1:2 complexes in o-DCB with affinities of around 105 M-1 alike to the [10]CPP⊃C60 reference system. A novel global analysis by combination of data sets from different techniques allowed us to follow the species distribution very precisely. ITC has proven to be a very powerful method for studying the complexation between fullerene derivatives and strained carbon nanohoops, which provides not only binding affinities and stoichiometries, but also all thermodynamic and kinetic parameters of the bis-pseudorotaxane formation. These results are of significant interest for the investigation of fullerene complexes in supramolecular chemistry and for their future applications in semiconductors and optoelectronics.

In this work, we compare for the first time the stability of [n]cycloparaphenylene ([n]CPP)-based host-guest complexes with Li+@C60 and C60 in the gas and the solution phase. Our gas-phase experiments...

The synthesis and characterization of four dumbbell‐shaped fullerene molecules connected by isosorbide and isomannide moieties is presented. Additionally, their electrochemical behavior and their ability to form complexes with [10]cycloparaphenylene ([10]CPP) were investigated. The cyclic voltammetry (CV) results of the fullerene dumbbells demonstrate a high electron affinity, indicating their strong interaction with electron‐donating counterparts such as carbon nanorings, which possess complementary charge and shape properties. To study the thermodynamic and kinetic parameters of complexation, isothermal titration calorimetry (ITC) was employed. NMR titration experiments provided further insights into the binding stoichiometries. Two distinct approaches were utilized to create bridged structures: one based on cyclopropane and the other based on furan. Regardless of the type of linker used, all derivatives formed conventional 2 : 1 complexes denoted as [10]CPP2⊃C60derivative. However, the methano‐dumbbell molecules exhibited distinct binding behavior, resulting in the formation of mono‐ and bis‐pseudorotaxanes, as well as oligomers (polymers). The formation of linear polymers holds significant potential for applications in solar energy conversion processes.

Crystal packing and chromophore communication are key parameters for the performance and functionality of many applications related to light‐energy harvesting and conversion. However, obtaining crystals of flexible and very soluble structures is troublesome. Nevertheless, a crystal structure of a highly flexible perylene‐3,4 : 9,10‐tetracarboxylic acid bisimide (PBI) cyclophane was obtained and analysed to compare the chromophore arrangement in the solid state with theconfiguration in solution as well as with calculated structures. The crystal structure exhibits an intra‐ and intermolecular slip‐stack arrangement of the heterochiral PBI units, forming a unique one‐dimensional π‐stacking supramolecular polymer‐like structure. These findings emphasize that the unique solid‐state arrangement of the chromophores cannot be easily predicted by elaborate studies in solution or by theoretical calculations. Furthermore, it features the importance of controlling the crystal packing to enable specific applications based on multiexciton generation processes where the spatial dependence and relative orientation of the chromophores are decisive parameters.

The cover picture represents the fascinating interaction between novel sugar‐bridged fullerene dumbbells and the [10]cycloparaphenylene nanoring. It visually depicts the formation of mono‐ and bis‐pseudorotaxanes, which exhibit variations depending on the sugar moiety and anchoring strategy employed. Additionally, the artwork highlights the formation of methano‐dumbbell oligomers, emphasizing their potential application in sustainable solar energy conversion. More information can be found in the Research Article by M. E. Pérez‐Ojeda, A. Mitrović, V. Maslak and co‐workers (DOI: 10.1002/chem.202301061).