Formation Of Host-guest Complexes Research Articles

Cyclic Oxothiomolybdates: Building Blocks for Cyclodextrin-Based Open Frameworks.

Desolvation processes, though common in self-assembled biological structures, are rarely evidenced and utilized in the design of crystalline architectures. In this study, we introduce a novel approach using the [Mo8S8O8(OH)8(guest)]2- complex, formed by the self-condensation of four [MoV 2O2S2]2- fragments around a guest unit (MoVIO6H4 or oxalate), as a chaotropic scaffold for crystallizing hybrid organic-inorganic systems with natural cyclodextrins. Our findings reveal that β-cyclodextrin (β-CD) facilitates the formation of host-guest complexes, while α-cyclodextrin (α-CD) induces the formation of a Kagome-type structure with significant voids. These new compounds were thoroughly characterized using X-ray diffraction (both powder and single-crystal), N2 adsorption, elemental and thermogravimetric analysis. Additionally, solution studies using 1H NMR titration and small-angle X-ray scattering (SAXS) demonstrated pre-association of the building units in solution. These results enhance our understanding of the design principles for supramolecular structures composed of inorganic polyanions and cyclodextrins.

Probing Noncovalent Interaction Strengths of Host-Guest Complexes Using Negative Ion Photoelectron Spectroscopy.

Noncovalent interactions (NCIs) are crucial for the formation and stability of host-guest complexes, which have wide-ranging implications across various fields, including biology, chemistry, materials science, pharmaceuticals, and environmental science. However, since NCIs are relatively weak and sensitive to bulk perturbation, direct and accurate measurement of their absolute strength has always been a significant challenge. This concept article aims to demonstrate the gas-phase electrospray ionization (ESI)-negative ion photoelectron spectroscopy (NIPES) as a direct and precise technique to measure the absolute interaction strength, probe nature of NCIs, and reveal the electronic structural information for host-guest complexes. Our recent studies in investigating various host-guest complexes that involve various types of NCIs such as anion-π, (di)hydrogen bonding, charge-separated ionic interactions, are overviewed. Finally, a summary and outlook are provided for this field.

Synthesis of π-Extended [1.1]Paracyclophanes, [1.1][n]PCP (n=2, 3, and 4), and Their Through-Space Conjugation.

[1.1][n]Paracyclophanes ([1.1][n]PCPs) (3) with n=2, 3, and 4, which consist of two [n]paraphenylene units connected by methylene bridges, were synthesized using short synthetic pathways with good overall yields. Single-crystal X-ray diffraction analyses reveal that the paraphenylene unit in 3 is bent, resulting in an elliptic core structure of 3. The facing bridgehead carbons of the paraphenylene units are separated by a distance much shorter than the sum of the van der Waals radii of sp2-carbon atoms. UV-vis absorption spectra, fluorescence spectra, electrochemical measurements, and theoretical calculations were used to demonstrate the presence of through-space (TS) conjugation in 3. Furthermore, host-guest complex formation between 3D (n=3) and tetracyanoquinodimethane in the solid state was revealed.

Structure Elucidation of Pharmaceutically Relevant Compounds Within Pyrene-Based Frameworks.

Single-crystal X-ray diffraction (SCXRD) is the preferred and most accurate technique for determining molecular structures. However, it can present challenges when dealing with specific small molecules and active pharmaceutical ingredients (APIs), as many do not form quality crystals without coformers or can be unstable. In this study, we introduce tetrakis(guanidinium) pyrenetetrasulfonate (G4PYR), a robust guanidinium-organosulfonate (GS) framework that efficiently encapsulates small molecules and APIs rich in functional groups. The hydrogen bonding frameworks formed by G4PYR display well-ordered structures with predictable pyrene-pyrene distances, making them ideally suited for targeting arene-based APIs with pendant groups. Successful encapsulation of various guests, including benzaldehyde, benzamide, and arenes containing multiple hydrogen bond donors and acceptors like uracil and thymine, was achieved. Furthermore, we successfully encapsulated important pharmaceutical and biologically relevant compounds, such as lidocaine, ropinirole, adenosine, thymidine, and others. Notably, we present a workflow for investigating host-guest complex formation using powder X-ray diffraction and high throughput experimentation.

Preferential Formation of Three-layered Host-Guest Complexes of a Planar Dinuclear Metallohost with Alkali Metal Ions.

We synthesized a planar macrocyclic dinuclear nickel(II) metallohost from the corresponding macrocyclic imine ligand containing two N2O2 chelate coordination sites and an O6 cation binding site like 18-crown-6 as well as peripheral hexyl groups. Due to the lipophilic nature of the hexyl groups, the metallohost was soluble in less polar media where its interaction with alkali metal ions was enhanced. The binding studies by NMR spectroscopy clearly showed its strong tendency to form multi-layered structures. The metallohost formed 2 : 1 and 1 : 1 (host/guest) complexes with Na+ with the two-step binding constants of logK1=6.6 and logK2=3.0. In contrast, its complexation with larger alkali metal ions (K+, Rb+, Cs+) preferentially gave 3 : 2 (host/guest) complexes when 2/3 equiv. of the guest was present. The three-layered structures of these 3 : 2 complexes were well characterized by mass spectrometry and 2D COSY/ROESY experiments as well as DFT calculations, elucidating their unique structural feature with three chemically different environments due to the oppositely curved two [Ni(saloph)] moieties of the metallohost. Therefore, the three-layered structures were preferentially formed when larger alkali metal ions (K+, Rb+, Cs+) were complexed with the metallohost.

Ligand-Directed Synthesis of a Self-Organized Chloro-Bridged Cubic Pd(II) Cage Showing Selective Encapsulation of Phenols.

The synthesis and guest recognition properties of a neutral Pd24-cubic cage, [{Pd3(NiPr)3PO}8(μ2-Cl)24] 1 are reported. The formation of the cubical assembly takes place by an exclusive one-pot ligand-assisted pathway directed by an oximido linker. The initial coordination of the oximido ligand pre-organizes the [Pd3(NiPr)3PO]3+ polyhedral building units into a tetrameric intermediate, which then transforms into an oximido-tethered tetrahedral assembly and to the cubical cage 1 in the presence of chloride ions. In the absence of the directing oximido linker, no cage formation was observed, and the Pd6-precursor was found to undergo self-condensation, giving rise to a new pentameric polyhedral cluster, [Pd5{(NiPr)3PO}2(OAc)2(OH)2] 2. The central cavity of the cube has been probed for guest encapsulation studies, which shows a high binding with phenolic guest molecules with association constants of the order of 104-105 M-1. The favorable formation of host-guest complexes was attributed to the strong hydrogen bonding interactions between the host and guest functional groups.

Preparation, characterization and heat release behavior of inclusion complexes formed between carvone or limonene and acyclic cucurbit[n]urils.

Carvone and limonene are naturally occurring monoterpenoids with unique aromas, making them valuable substances in synthetic fragrance production. However, their application is limited due to low stability and rapid volatilization. To address this challenge, host-guest complexes offer a promising solution. In this study, two acyclic cucurbit[n]urils were synthesized to form inclusion complexes with carvone and limonene, aiming to enhance their thermal stability and achieve excellent heat release properties. The binding behavior of the complexes was investigated using NMR, X-ray diffraction (XRD), Fourier transform infrared (FTIR) and molecular bonding analyses, confirming the formation of host-guest inclusion complexes. Our study successfully prepared four inclusion complexes (M1/CA, M2/CA, M1/LI, M2/LI) and characterized them using NMR, XRD and FTIR techniques. These complexes exhibited a 1:1 stoichiometric ratio, and their binding constants were determined through fluorescence titration. The thermal controlled release experiment shows that the degree of carvone and limonene release is different with a change of temperature, indicating that the inclusion complexes have good thermally controlled release performance, and the thermal release retention rate has a certain correlation with KS value. The larger the KS value, the higher the thermal release retention rate of the inclusion complexes, the lower the volatilization of the inclusion complexes, the longer the retention time and the better the thermal stability. This study presents a novel approach for developing carvone- and limonene-based fragrances, expanding their application potential in various industries. © 2024 Society of Chemical Industry.

Supramolecular Chemistry of Polymer-Based Molecular Tweezers: A Minireview

Polymer-based molecular tweezers have emerged as a prominent research area due to their enhanced ability to form host–guest complexes, driven by advancements in their design and synthesis. The impact of the spacer structure on the tweezers is predominant. They can be rigid, flexible, and stimuli-responsive. Herein, a new generation of molecular tweezers is introduced as polymer-based molecular tweezers. The integration of molecular tweezers onto biopolymers has significantly expanded their potential applications, making them promising candidates, especially in drug delivery, owing to their biocompatibility, adaptive structural features, and versatile interaction capabilities. The unique structure of polymer-based molecular tweezers, particularly when integrated with biopolymers, creates a unique nano-environment that enhances their interaction with guest molecules. This minireview focuses on the synthesis and applications of polymer-based molecular tweezers and examines how the incorporation of various spacers affects their binding affinity and specificity. These features highlight the advancement of these polymer-based systems, emphasizing their potential applications, particularly in drug delivery, water treatment technology, and future research opportunities.

Guest-Mediated Modulation of Photophysical Pathways in a Coronene Bisimide Cyclophane.

The properties and functions of chromophores utilized by nature are strongly affected by the environment formed by the protein structure in the cells surrounding them. This concept is transferred here to host-guest complexes with the encapsulated guests acting as an environmental stimulus. A new cyclophane host based on coronene bisimide is presented that can encapsulate a wide variety of planar guest molecules with binding constants up to (4.29 ± 0.32) × 1010 M-1 in chloroform. Depending on the properties of the chosen guest, the excited state deactivation of the coronene bisimide chromophore can be tuned by the formation of host-guest complexes toward fluorescence, exciplex formation, charge separation, room-temperature phosphorescence (RTP), or thermally activated delayed fluorescence (TADF). The photophysical processes were investigated by UV/vis absorption, emission, and femto- and nanosecond transient absorption spectroscopy. To enhance the TADF, two different strategies were used by employing suitable guests: the reduction of the singlet-triplet gap by exciplex formation and the external heavy atom effect. Altogether, by using supramolecular host-guest complexation, a versatile multimodal chromophore system is achieved with the coronene bisimide cyclophane.

Excited-State Dynamics of a Bright Fluorescent Dye with Precise Control of Emission Color Using Acid-Base Equilibrium, Intramolecular Charge Transfer, and Host-Guest Chemistry.

A fluorescent dye, a dithiophene-conjugated benzothiazole derivative (DTBz), was prepared to have high fluorescence emission quantum yields (ΦF) across various organic solvents. Its emission color modulation, from bright blue to deep red, was achieved through intramolecular charge transfer (ICT), acid-base equilibrium, and host-guest chemistry. Although it exhibits a weak solvatochromic effect, DTBz exhibited a bright fluorescence emission around 480 nm upon excitation at 390 nm in most solvents. In polar solvents, such as MeOH (methanol), EtOH (ethanol), DMF (N,N-dimethylforamide), and DMSO (dimethyl sulfoxide), an additional ICT emission band emerged around 640 nm, notably intense in DMSO, resulting in a bright greenish-white emission (ΦF = 0.67). The addition of 1,8-diazabicyclo[5,4.0]undec-7-ene (DBU) altered emission characteristics, reducing emission from the local excited (LE) state and enhancing ICT state emission. The degree of emission spectral change saturation with DBU addition varied with the solvent nature. Polar solvents with high dielectric constants, like DMSO and DMF, saw a complete disappearance of LE state emission with 5 equiv of DBU, resulting in a deep red emission (ΦFs of 0.53 and 0.48, respectively). Femtosecond transient absorption spectroscopy and time-resolved photoluminescence measurements elucidated the excited-state dynamics, revealing a long-lived excited state (τ-H = 10.3 ns) at a lower energy emission (640 nm), identified as DTBz-*, supported by transient absorption spectra analysis. Further analysis, including time-resolved fluorescence decay measurements and time-dependent density-functional theory (TD-DFT) calculations, underscored the role of deprotonation of DTBz's hydroxyl group in promoting the ICT process. The CIE coordination plot demonstrated wide linear emission color changes upon successive DBU additions in all solvents, while emission color precision was achieved through host-guest chemistry. Emission changes induced by DBU were reverted to the original state upon beta-cyclodextrin (β-CD) addition, with the 1H NMR study revealing the competition between acid-base equilibrium and host-guest complex formation as the cause of emission color change.

Nucleosides as Organizing Architectural Moieties

Chemistry “beyond the molecule” is epitomized in nature by a plethora of relatively weak noncovalent interactions. The three-dimensional structures of most biopolymers are controlled with noncovalent interactions, either between different parts of the same strand (as in protein α-helices) or between two separate strands (as in the DNA duplex and protein β-sheet). While nature has refined the construction of biopolymers, our mastery of the subtle noncovalent interactions as synthetic tools is in an early stage of development. Only in the past two decades people begun to develop ways of mimicking the natural light-harvesting complexes by noncovalent assembly of porphyrin units aiming to obtain favored spacing and orientation between the chromophores. The construction of multi-chromophoric assemblies has led to resurgence of interest in coordination chemistry due to formation of ordered arrays directed through molecular recognition events. As a module in the construction of supramolecular assemblies, porphyrins and metallo-porphyrins can be exploited in two different ways: porphyrins can behave as donor building blocks insofar as they comprise meso-substituents, such as pyridyl groups, which can act as ligands that can suitably coordinate to metal cations, while metalloporphyrins can act as acceptor building blocks as soon as the metal atom inside the porphyrin core has at least one axial site available for coordination. For the last years, we have focussed on cofacial bis-porphyrin tweezers for host/guest interactions and investigated the possibilty to obtain self-coordinated molecular systems with predictable spectral and redox characteristics. We report here the synthesis of a di-nucleotide bearing pendant porphyrins dedicated to adopt a pre-organized coformation with face-to-face porphyrins, and capable to self-organize in a stable sandwich type complexe with bidentate base such as DABCO.1 Using a similar strategy as the one used in antisense research, an artificial nucleotidic backbone was built from modified deoxy-uridine units linked with a more rigid linker than the phosphodiester moieties found in natural oligonucleotides. Antisense research uses modified oligonucleotides, less flexible than natural strands, to pre-organize the system toward the obtaining of stable double helices between synthesized and natural oligonucleotides. A modified oligonucleotidic backbone was here used to target a parallel conformation of the porphyrins appended to each deoxy-uridine moiety. To provide a rigid environment for the porphyrins, the uridine units were coupled in 3’-5’ stepwise fashion using ether-ester type of spacer of suitable length, and porphyrins were anchored to the uridine by means of robust carbon-carbon bonds.Earlier studies demonstrated that a peptidic linker doesn’t provide sufficient pre-organization to enhance significantly the association constant with bidentate bases such as DABCO on the contrary of some flexible linkers such as uridine or 2’-deoxyuridine. We document herein that the gain in stability for the formation of sandwich type host-guest complex with DABCO can be even greater when a dinucleotide linker is used. Such pre-organization increases the association constants by one to two orders of magnitude when compared to the association constants of the same bidentate ligands with a reference Zn(II) porphyrin. Comparison of these results with those obtained for rigid tweezers shows a better efficiency of the flexible nucleosidic dimers.We thus document the fact that the choice of rigid spacers is not the only way to pre-organize bis-porphyrins, and that some well-chosen nucleosidic linkers offer an interesting option for the synthesis of such devices. Furthermore, the chirality and enantio-purity of the nucleosidic linkers paves the way toward the selective complexation of enantio-pure bidentate guests and the resolution of racemates. Acknowledgements This work was supported by the CNRS and the French Ministry of Research. References Solladié, R. Rein, S. Bouatra, S. Merkas, C. Sooambar, I. Piantanida, M. Žinić, J. Porphyrins Phthalocyanines 2020, 24, 636-645.

Following the Trace of Cyclodextrins on the Selenium and Tellurium Odyssey.

There is an urgent need to develop safer and more effective modalities for the treatment of numerous pathologies due to the increasing rates of drug resistance, undesired side effects, poor clinical outcomes, etc. Over the past decades, cyclodextrins (CDs) have gathered great attention as potential drug carriers due to their ability to enhance their bioactivities and properties. Likewise, selenium (Se) and tellurium (Te) have been extensively studied during the last decades due to their possible therapeutical applications. Although there is limited research on the relationship between Se and Te and CDs, herein, we highlight different representative examples of the advances related to this topic as well as give our view on the future directions of this emerging area of research. This review encompasses three different aspects of this relationship: (1) modification of the structure of the different CDs; (2) formation of host-guest interaction complexes of naïve CDs with Se and Te derivatives in order to overcome specific limitations of the latter; and (3) the use of CDs as catalysts to achieve novel Se and Te compounds.

2,3 : 6,7-Naphthalene Bis(dicarboximide) Cyclophane: A Photofunctional Host for Ambient Delayed Fluorescence in Solution.

Harvesting triplet excitons of heavy atom-free purely organic chromophores under aerated conditions is challenging due to the quenching of long-lived triplet states by molecular oxygen and vibrational dissipation. Herein, we show a supramolecular approach of triplet harvesting via mitigating quenching pathways of a triplet harvester. Specifically, we used a host-guest system based on 2,3 : 6,7-naphthalene bis(dicarboximide)-derived cyclophane (NBICy) and carbazole derivative (EtCz). Complexation studies and single-crystal X-ray analysis showed the formation of a rigid host-guest complex (K≈104 M-1 in CCl4), resulting in triplet-exciton stabilization under aerated conditions via mitigating vibrational interference and oxygen quenching. Photophysical studies elucidate the delayed fluorescence emission from the charge-transfer state (1CT) with a quantum yield (QY) of 6-8 % under ambient conditions which increased up to 36 % in an inert atmosphere.

Dexamethasone-loaded ROS stimuli-responsive nanogels for topical ocular therapy of corneal neovascularization

Dexamethasone (DEX) has been demonstrated to inhibit the inflammatory corneal neovascularization (CNV). However, the therapeutic efficacy of DEX is limited by the poor bioavailability of conventional eye drops and the increased risk of hormonal glaucoma and cataract associated with prolonged and frequent usage. To address these limitations, we have developed a novel DEX-loaded, reactive oxygen species (ROS)-responsive, controlled-release nanogel, termed DEX@INHANGs. This advanced nanogel system is constructed by the formation of supramolecular host-guest complexes by cyclodextrin (CD) and adamantane (ADA) as a cross-linking force. The introduction of the ROS-responsive material, thioketal (TK), ensures the controlled release of DEX in response to oxidative stress, a characteristic of CNV. Furthermore, the nanogel's prolonged retention on the corneal surface for over 8 h is achieved through covalent binding of the integrin β1 fusion protein, which enhances its bioavailability. Cytotoxicity assays demonstrated that DEX@INHANGs was not notably toxic to human corneal epithelial cells (HCECs). Furthermore, DEX@INHANGs has been demonstrated to effectively inhibit angiogenesis in vitro. In a rabbit model with chemically burned eyes, the once-daily topical application of DEX@INHANGs was observed to effectively suppress CNV. These results collectively indicate that the nanomedicine formulation of DEX@INHANGs may offer a promising treatment option for CNV, offering significant advantages such as reduced dosing frequency and enhanced patient compliance.

In Ukrainian

Due to the variety of their forms and properties, silver nanoparticles (AgNPs) are promising for obtaining nanomaterials with various functional applications. Today, regardless of the method of obtaining AgNPs, there is a problem of stabilizing their surface to prevent aggregation, which significantly reduces their activity and prevents uniform distribution during the preparation of nanomaterials. The aim of this work was the synthesis of silver nanoparticles using an oligomeric ionic liquid (OIL) and the study of their structure and antimicrobial properties. In this work, for the first time, an anionic OIL with a hyperbranched structure developed by us was used as a surface stabilizer in the synthesis of AgNPs. The synthesis of AgNPs was carried out by the reduction of Ag ions in the composition of AgNO3 with trisodium citrate in the presence of this OIL. Using the methods ofUV-vis and FTIR spectroscopy, X-ray analysis, electron microscopy and the disc-diffusion method, the peculiarities of the structural organization of AgNPs and their antimicrobial properties were studied. UV-visible spectroscopy data indicate the formation of silver nanoparticles and their spherical or quasi-spherical shape. It was found that there are adsorbed ionic and carbonyl groups on the surface of the formed AgNPs, and the formation of host-guest complexes between OIL and silver ions was revealed using FTIR. The formation of AgNPs and complexes between OIL and silver ions is also confirmed by X-ray diffraction. According to electron microscopy, the size of the synthesized nanoparticles varies from 5 to 16 nm, with an average value of 10.2 nm. This average value is very close to the value of 9.3 nm obtained from the results of X-ray analysis. The synthesized silver nanoparticles showed a very high antimicrobial activity against C. albicans fungi, while the width of the inhibition zone (d) was 34 mm. Also, the AgNPs powder shows very high activity against gram-positive bacteria S. aureus (d = 30 mm) and gram-negative bacteria E. coli (d = 12 mm). The approach developed by us to the synthesis of AgNPs in the presence of OIL as a surface stabilizer with certain functionalization of the latter opens up new opportunities in the synthesis of AgNPs and the preparation of highly dispersed related systems, including functionalized nanocomposite polymer materials with antimicrobial properties.

Chirality Sensing of Cryptochiral Guests with Prism[n]arenes.

Optical chirality sensing has gained significant attention in recent years. Within this field, the quest for stereodynamic chiroptical probes capable of detecting cryptochiral guests presents a formidable challenge. Macrocycles exhibiting planar chirality have emerged as promising candidates for amplifying the chirality of cryptochiral guests. In this study, we demonstrate that the formation of host-guest complexes between cryptochiral molecules and planar chiral prismarenes triggers electronic circular dichroism (ECD) signals via host-guest complexation-induced chirality amplification. The absolute configuration of the most stable chiral macrocyclic host-guest complex has been established by resorting to both exciton model and DFT computations. Furthermore, we demonstrated that this supramolecular chirality sensing system can be employed to determine the enantiomeric composition of scalemic mixtures by measuring the ECD bands intensity. The information described here opens the way for the use of prismarenes as stereodynamic probes for sensing of cryptochiral guests.

Easy and Effective Method for α-CD:N2O Host-Guest Complex Formation.

α-CD:N2O "host-guest" type complexes were formed by a simple solid-gas reaction (N2O sorption into α-CD) under different gas pressures and temperatures. The new N2O inclusion method applied in the present study was compared with the already known technique based on the crystallization of clathrates from a water solution of α-CD saturated with N2O. A maximum storage capacity of 4.5 wt.% N2O was achieved when charging the cyclodextrin from a gas phase. The amount of included gas decreases to 1.3 wt.% when the complex is stored in air at 1 atm and room temperature, analogous to that achieved by the crystallization of α-CD:N2O. Furthermore, it was shown that the external coordination of N2O to either the upper or lower rim of α-CD without hydration water displacement is the preferred mode of binding, due to hydrogen bonds with neighboring -OH groups from the host macrocycle and three of the hydration water molecules nearby. The capacity of α-CD to store N2O and the thermal stability of the α-CD:N2O complex demonstrated promising applications of these types of complexes in food and beverages.

Effect of Crown Ether Additives on the Enhanced Performance of Metallic Bipolar Plates for Proton Exchange Membrane Fuel Cells.

One of the key components of the fuel cell stack is a metallic bipolar plate (MBP) that plays multiple roles, such as current collector, fuel and oxidant distributor, and mechanical support. However, corrosion and consequent metal elution are major drawbacks of the MBP because they diminish the efficiency and power performance of membrane-electrode assemblies (MEAs). Herein, we show that the crown ether (CE) additive can simultaneously inhibit surface corrosion of the MBP and act as a scavenger for eluted metal ions to alleviate contamination of other components. From the electrochemical measurement, high-resolution imaging, and elemental analysis, we have found that the CE undergoes electrolytic decomposition and makes an efficient protective layer in an in situ manner. This layer prevents direct contact between the MBP and electrolyte as well as the dissolution of metal ions into the electrolyte. In addition, we demonstrate that the CE can improve the recovery protocol of the MEA owing to the formation of host-guest complexes between the CE and metal cations. These results provide key insights into the design of high-performance MBPs for proton-exchange membrane fuel cells.

Bidentate boron Lewis acids: synthesis by tin boron exchange reaction and host-guest complex formation.

Four bidentate boron Lewis acids based on the 1,8-diethynylanthracene backbone have been synthesized by a tin-boron exchange reaction with various chloroboranes, yielding the products in good to excellent yields. Complexation experiments of the host compounds with pyridine, pyrimidine and TMEDA demonstrated striking differences in terms of formation and solubility of the supramolecular adducts. The host-guest complexes were investigated by multinuclear NMR spectroscopy and structurally characterized by X-ray diffraction experiments, illustrating the adaptation of the host system upon adduct formation with different neutral guest molecules.

Stability of [10-12]cycloparaphenylene complexes with pristine fullerenes C76,78,84 and endohedral metallofullerenes M3N@C78,80.

[n]Cycloparaphenylenes ([n]CPPs) are strained macrocycles, comprising only sp2-hybridized carbon atoms. In recent years, [n]CPPs have become of great research interest in the field of supramolecular chemistry since their special structure enables the formation of novel host-guest complexes. In this work, we investigate the gas-phase chemistry of noncovalent complexes of [10-12]CPP with the pristine fullerenes C76/78/84 and the endohedral metallofullerenes (EMFs) Sc3N@D3h-C78, Sc3N@D5h-C80 and M3N@Ih-C80 (M = Sc, Y, Lu, Gd). The [1 : 1] complexes with [10-12]CPP are detected as radical cations. The stability and charge distributions of these complexes are studied using energy-resolved collision-induced dissociation (ER-CID). Our results assess the size complementarity, the influence of fullerene symmetry and size as well as the role of the metal size inside the EMF on the binding affinity and complex stability. Two main trends in complex stability have been found: First, [10-12]CPP form more stable complexes with EMFs than with pristine fullerenes and second, all complexes of EMFs with the C80 skeleton show similar stability despite the different metal clusters encapsulated. Another major finding is the fact that [11]CPP is generally the most suitable host for fullerenes with a C76/78/80/84 skeleton. Considering the charge distributions, we observe the existence of two different fragmentation channels for complexes with EMFs where the radical cation is either located at the CPP or at the EMF: (1) [n]CPP+˙ + EMF and (2) [n]CPP + EMF+˙. This behavior allows a clear distinction of the cage isomers ([11]CPP⊃Sc3N@Ih-C80)+˙ and ([11]CPP⊃Sc3N@D5h-C80)+˙ in the MS2 experiment. The experimental results are accompanied by density functional theory (DFT) calculations of ionization potentials (IPs) and fragmentation energies. The computational results fully confirm the measured order of complex stabilities and explain the prevalence of EMF or CPP signals in the spectra by the trend in ionization potentials.