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We report the implementation of the analytical Hessian for the mechanochemical extended hydrostatic compression force field method in the Q-Chem program package. To verify the implementation, the analytical Hessian was compared with finite difference calculations. In addition, we calculated the pressure dependency of the Raman active vibrational modes of methane, ethane, and hydrogen, as well as all IR and Raman active modes of Buckminsterfullerene, and compared the results with experimental and theoretical data. Our implementation paves the way for the analysis of geometric points on a pressure-deformed potential energy surface and provides a straightforward model to calculate the vibrational properties of molecules under high pressure. [ABSTRACT FROM AUTHOR]

A novel implementation of the coupled-cluster singles and doubles (CCSD) approach is presented that is specifically tailored for the treatment of large symmetric systems. It fully exploits Abelian point-group symmetry and the use of the Cholesky decomposition of the two-electron repulsion integrals. In accordance with modern CCSD algorithms, we propose two alternative strategies for the computation of the so-called particle–particle ladder term. The code is driven toward the optimal choice depending on the available hardware resources. As a large-scale application, we computed the frozen-core correlation energy of buckminsterfullerene (C60) with a polarized valence triple-zeta basis set (240 correlated electrons in 1740 orbitals). [ABSTRACT FROM AUTHOR]

In this contribution, we employ computational tools from the energy landscape approach to test Gaussian Approximation Potentials (GAPs) for C60. In particular, we apply basin-hopping global optimization and explore the landscape starting from the low-lying minima using discrete path sampling. We exploit existing databases of minima and transition states harvested from previous work using tight-binding potentials. We explore the energy landscape for the full range of structures and pathways spanning from the buckminsterfullerene global minimum up to buckybowls. In the initial GAP model, the fullerene part of the landscape is reproduced quite well. However, there are extensive families of C1@C59 and C2@C58 structures that lie lower in energy. We succeeded in refining the potential to remove these artifacts by simply including two minima from the C2@C58 families found by global landscape exploration. We suggest that the energy landscape approach could be used systematically to test and improve machine learning interatomic potentials. [ABSTRACT FROM AUTHOR]

In this contribution, we employ computational tools from the energy landscape approach to test Gaussian Approximation Potentials (GAPs) for C60. In particular, we apply basin-hopping global optimization and explore the landscape starting from the low-lying minima using discrete path sampling. We exploit existing databases of minima and transition states harvested from previous work using tight-binding potentials. We explore the energy landscape for the full range of structures and pathways spanning from the buckminsterfullerene global minimum up to buckybowls. In the initial GAP model, the fullerene part of the landscape is reproduced quite well. However, there are extensive families of C1@C59 and C2@C58 structures that lie lower in energy. We succeeded in refining the potential to remove these artifacts by simply including two minima from the C2@C58 families found by global landscape exploration. We suggest that the energy landscape approach could be used systematically to test and improve machine learning interatomic potentials. [ABSTRACT FROM AUTHOR]

Phosphorene and fullerene are representative two‐dimensional (2D) and zero‐dimensional (0D) nanomaterials respectively, constructing their heterodimensional hybrid not only complements their physiochemical properties but also extends their applications via synergistic interactions. This is however challenging because of their diversities in dimension and chemical reactivity, and theoretical studies predicted that it is improbable to directly bond C60 onto the surface of phosphorene due to their strong repulsion. Here, we develop a facile electrosynthesis method to synthesize the first phosphorene‐fullerene hybrid featuring fullerene surface bonding via P−C bonds. Few‐layer black phosphorus nanosheets (BPNSs) obtained from electrochemical exfoliation react with C602− dianion prepared by electroreduction of C60, fulfilling formation of the "improbable" phosphorene‐fullerene hybrid (BPNS‐s‐C60). Theoretical results reveal that the energy barrier for formation of [BPNS‐s‐C60]2− intermediate is significantly decreased by 1.88 eV, followed by an oxidization reaction to generate neutral BPNS‐s‐C60 hybrid. Surface bonding of C60 molecules not only improves significantly the ambient stability of BPNSs, but also boosts dramatically the visible light and near‐infrared (NIR) photocatalytic hydrogen evolution rates, reaching 1466 and 1039 μmol h−1 g−1 respectively, which are both the highest values among all reported BP‐based metal‐free photocatalysts. [ABSTRACT FROM AUTHOR]

Directed transportation of materials at molecular scale is important due to its crucial role in the development of nanoelectromechanical devices, particularly the directional movements along the carbon nanotubes (CNTs), due to the applications of CNTs as nano-manipulators, confined reactors, and drug or other materials delivery systems. In the present investigation, we evaluate the movements of C60 fullerenes on the surface of the cone-shaped CNTs. The fullerene molecules indicate directed motion toward the narrower end of CNTs, which is due to the potential energy gradient along the nanotube length. A continuum model is proposed to evaluate the mechanism of the directed motion and the results of the theoretical model are compared with numerical simulations. Directed movements have been examined at various opening angles of CNTs, considering the trajectories of motions, variation of potential energy, and diffusion coefficients. At smaller opening angles, the driving force on the C60 increases and the molecule experiences more directed transport along the nanotube. The motion of fullerene has also been simulated inside the cone-shaped CNTs, with similar opening angle, and different average radius. At lower average radius of the cone-like nanotubes, the motion of C60 is comparatively more rectilinear. Directional transport of fullerene has been observed in the opposite direction, when the molecule moves on the external surface of the cone-like CNTs, which is due to the stronger interaction of C60 with the parts of the external surface with larger radius. The effect of temperature has been evaluated by performing the simulations at the temperature range of 100 to 400 K. The direction of the velocity reveals that the thermal fluctuations at higher temperatures hinder the directed motion of molecule along the cone-shaped CNTs. The results of the present study propose a new method to obtain directed transport of molecules which can be helpful in different applications such as drug delivery systems. [ABSTRACT FROM AUTHOR]

Buckyballs are closed spherical carbon cages which are beneficial in several industries. Their chemical graphs provide structural invariants called topological invariants. This study is devoted to investigating the relation between degree-based topological index called Sombor index and physical properties of buckyballs. The sample contains buckyballs consisting of 54, 58, 60, 70, 74, 76, 78, 80, 82, 84, 86 and 90 carbon atoms.The topological indices with degree bases can be used to display the physical characteristics of buckyballs. The numerical values of topological indices describe the topological structure of a molecule. The physical properties include binding energy, Ramsauer–Townsend effect (RT-1, RT-2), shape resonances (SR-1, SR-2), and heat of formation of buckyballs. [ABSTRACT FROM AUTHOR]

The whimsical Las Vegas/Monte Carlo cubic dice are generalized to construct the combinatorial problem of enumerating all n-dimensional hypercube dice and dice of other shapes that exhibit cubic, icosahedral, and higher symmetries. By utilizing powerful generating function techniques for various irreducible representations, we derive the combinatorial enumerations of all possible dice in n-dimensional space with hyperoctahedral symmetries. Likewise, a number of shapes that exhibit icosahedral symmetries such as a truncated dodecahedron and a truncated icosahedron are considered for the combinatorial problem of dice enumerations with the corresponding shapes. We consider several dice with cubic symmetries such as the truncated octahedron, dodecahedron, and Rubik's cube shapes. It is shown that all enumerated dice are chiral, and we provide the counts of chiral pairs of dice in the n-dimensional space. During the combinatorial enumeration, it was discovered that two different shapes of dice exist with the same chiral pair count culminating to the novel concept of isochiral polyhedra. The combinatorial problem of dice enumeration is generalized to multi-coloring partitions. Applications to chirality in n-dimension, molecular clusters, zeolites, mesoporous materials, cryptography, and biology are also pointed out. Applications to the nonlinear n-dimensional hypercube and other dicey encryptions are exemplified with romantic, clandestine messages: "I love U" and "V Elope at 2". [ABSTRACT FROM AUTHOR]

Molecular iron phthalocyanine (FePc) bearing a single‐atom Fe–N4 moiety is a high‐profile non‐platinum catalyst toward the oxygen reduction reaction (ORR), but its unsatisfactory activity and inadequate stability hinder the practical application. Herein, a novel strategy by hybridizing FePc with fullerene‐derived intrinsic defect‐rich carbon to improve its ORR activity and stability is reported. Via alkali‐assisted thermal pyrolysis, C60 molecules are disintegrated into tiny fragments that then restructure into pentagon‐ and edge‐rich carbon (FC). Utilizing FC as a support of FePc leads to a significantly improved ORR activity compared to other supports including reduced graphene oxide and carbon nanotube that hold distinct structural features. The optimized FePc/FC with a Fe loading of 3 wt% presents a half‐wave potential of 0.917 V, far beyond that of Pt/C (0.846 V), via selective four‐electron ORR pathway and excellent stability under accelerated stress test. The practical applicability of FePc/FC is also demonstrated as a high‐performing cathode catalyst of aqueous zinc–air batteries. It is, for the first time, explicitly disclosed that strong interactions between FePc molecules and intrinsic carbon defects (e.g., pentagons and edges) not only strengthen the anchoring effect of supported FePc but also enhance the intrinsic ORR activity of single‐atom Fe–N4 sites. [ABSTRACT FROM AUTHOR]

Developing advanced electrocatalysts is crucial for alkaline hydrogen evolution reaction (HER). A balance in adsorption energy for each reaction intermediate on the catalyst determines the overall catalytic rate. This balance is closely linked to the d‐band center, which is, in turn, controlled by the electronic structure of the active sites. Herein, C60 molecules with electron‐withdrawing properties and manganese (Mn) atoms with electron‐donating properties to drive charge redistribution on Ru active sites are strategically utilized. The synergistic and complementary effects of C60 and Mn regulate the d‐band centers of Ru sites to an optimal position, optimizing both the water adsorption and hydrogen desorption of the synthesized Ru catalysts. The constructed MnRu/C60‐3 catalyst exhibits a low overpotential of 8 mV at 10 mA cm−2, a large TOF value of 15.5 s−1, and a high mass activity of 2.39 A mg−1Ru at an overpotential of 100 mV in 1.0 m KOH. The anion exchange membrane water electrolyzer, assembled with MnRu/C60‐3 as the cathode, demonstrates excellent water electrolysis performance and high stability under industrial operational conditions. This work offers a fresh perspective on catalyst design principles by manipulating the d‐band centers of active sites using two complementary components. [ABSTRACT FROM AUTHOR]

Graphene is used as a growth template for van der Waals epitaxy of organic semiconductor (OSC) thin films. During the synthesis and transfer of chemical‐vapor‐deposited graphene on a target substrate, local inhomogeneities in the graphene—in particular, a nonuniform strain field in the graphene template—can easily form, causing poor morphology and crystallinity of the OSC thin films. Moreover, a strain field in graphene introduces a pseudo‐electric field in the graphene. Here, the study investigates how the strain and strain‐induced pseudo‐electric field of a graphene template affect the self‐assembly of π‐conjugated organic molecules on it. Periodically strained graphene templates are fabricated by transferring graphene onto an array of nanospheres and then analyzed the growth and nucleation behavior of C60 thin films on the strained graphene templates. Both experiments and a numerical simulation demonstrated that strained graphene reduced the desorption energy between the graphene and the C60 molecules and thereby suppressed both nucleation and growth of the C60. A mechanism is proposed in which the strain‐induced pseudo‐electric field in graphene modulates the binding energy of organic molecules on the graphene. [ABSTRACT FROM AUTHOR]

We have developed novel polynomials called delta polynomials, which are, in turn, derived from the characteristic and matching polynomials of graphs associated with polycyclic aromatic compounds. Natural logarithmic aromatic indices are derived from these delta polynomials, which are shown to provide new insights into the aromaticity of polycyclic aromatic compounds, including the highly symmetric C60 buckminsterfullerene, several other fullerenes, graphene, kekulene series and other cycloarenes, such as polycyclic circumcoronaphenes and coronoids. The newly developed aromatic index yields a value of 6.77 for graphene, 6.516865 for buckminsterfullerene C60(Ih), 5.914023 for kekulene (D6h symmetry), 6.064420 for coronene (D6h), 6.137828 for circumcoronene (D6h), 6.069668 for dicronylene and so forth. Hence, the novel scaled logarithmic aromatic delta indices developed here appear to provide good quantitative measures of aromaticity, especially when they are used in conjunction with other aromatic indicators. [ABSTRACT FROM AUTHOR]

The thermal stability of fullerenes plays a fundamental role in their synthesis and in their thermodynamic and kinetic properties. Here, we perform extensive molecular dynamics (MD) simulations using an accurate machine-learning-based Gaussian Approximation Potential (GAP-20) force field to investigate the energetic and thermal properties of the entire set of 1812 C 60 isomers. Our MD simulations predict a comprehensive and quantitative correlation between the relative isomerization energy distribution of the C 60 isomers and their thermal fragmentation temperatures. We find that the 1812 C 60 isomers span over an energetic range of over 400 kcal mol − 1 , where the majority of isomers (∼ 85%) lie in the range between 90 and 210 kcal mol − 1 above the most stable C 60 - I h buckminsterfullerene. Notably, the MD simulations show a clear statistical correlation between the relative energies of the C 60 isomers and their fragmentation temperature. The maximum fragmentation temperature is 4800 K for the C 60 - I h isomer and 3700 K for the energetically least stable isomer, where nearly 80% of isomers lie in a temperature window of 4000–4500 K. In addition, an Arrhenius-based approach is used to map the timescale gap between simulation and experiment and establish a connection between the MD simulations and fragmentation temperatures. [ABSTRACT FROM AUTHOR]

Excitons are realizations of a correlated many-particle wave function, specifically consisting of electrons and holes in an entangled state. Excitons occur widely in semiconductors and are dominant excitations in semiconducting organic and low-dimensional quantum materials. To efficiently harness the strong optical response and high tuneability of excitons in optoelectronics and in energy-transformation processes, access to the full wavefunction of the entangled state is critical, but has so far not been feasible. Here, we show how time-resolved photoemission momentum microscopy can be used to gain access to the entangled wavefunction and to unravel the exciton's multiorbital electron and hole contributions. For the prototypical organic semiconductor buckminsterfullerene (C60), we exemplify the capabilities of exciton tomography and achieve unprecedented access to key properties of the entangled exciton state including localization, charge-transfer character, and ultrafast exciton formation and relaxation dynamics. Understanding excitonic optical excitations is integral to improving optoelectronic and photovoltaic semiconductor devices. Here, Bennecke et al. use photoemission exciton tomography to unravel the multiorbital electron and hole contributions of entangled excitonic states in the prototypical organic semiconductor C60. [ABSTRACT FROM AUTHOR]

Oxidative damage is one of the recognized contributors to cell and animal aging. In contrast, antioxidants are natural substances that work to prevent or at least delay this type of cell damage, incorporating the production of free radicals and oxidation. Concerning this study, we will explore the antioxidant Buckminsterfullerene (C60) to associate these positive effects with C60. This interdisciplinary analysis aims to integrate the studies of Chemistry and Biology to perform a meticulous experiment on how the efficacy of nutritive oils on cell longevity and regeneration is impacted when mixed with Buckminsterfullerene, precisely on the mice strain C57BL/6J. Combining C60 with salmon oil and olive oil creates five separate study groups, including a control group. The main findings were that the Salmon Oil C60 group contained the mice with the highest number of months lived on average, with the most significant percentage increase in longevity compared to the control group (Dry Kibble). The antioxidant successfully maintained a healthy mouse for a more extended period, which holds implications for extending the human lifespan, given further research. [ABSTRACT FROM AUTHOR]

High resolution force measurements of molecules on surfaces, in non-contact atomic force microscopy, are often only performed at cryogenic temperatures, due to needing a highly stable system, and a passivated probe tip (typically via CO-functionalisation). Here we show a reliable protocol for acquiring three-dimensional force map data over both single organic molecules and assembled islands of molecules, at room temperature. Isolated cobalt phthalocyanine and islands of C60 are characterised with submolecular resolution, on a passivated silicon substrate (B:Si(111)- ( 3 × 3 ) R 3 0 ∘ ). Geometries of cobalt phthalocyanine are determined to a ~ 10 pm accuracy. For the C60, the protocol is sufficiently robust that areas spanning 10 nm × 10 nm are mapped, despite the difficulties of room temperature operation. These results provide a proof-of-concept for gathering high-resolution three-dimensional force maps of networks of complex, non-planar molecules on surfaces, in conditions more analogous to real-world application. High resolution force measurements of molecules on surfaces using non-contact atomic force microscopy are typically performed at cryogenic temperatures. Here, the authors outline a reliable protocol for acquiring three-dimensional force map data at room temperature, demonstrating such capabilities on isolated cobalt phthalocyanine molecules and islands of C60 molecules. [ABSTRACT FROM AUTHOR]

The capacity for nanopatterning and functionality is a promising facet of supramolecular self‐assembly. However, the formation of molecular frameworks entirely dependent on van der Waals (vdW) interactions is infrequently explored. Herein, 2D vdW supramolecular structures are synthesized through the self‐assembled cocrystallization of C60 and decanethiol (DT) molecules on Au(111) surface. Notably, the system eliminates the need of functional groups for specific bonding between adjacent units. The conformation C60/DT is delicately manipulated by adjusting molecular coverage and annealing temperature. The absence of directional bonding between C60 and DT molecules facilitates the formation of a variety of stable phases at room temperature (RT), such as 1) porous C60 networks with thiol‐filled pores and 2) self‐synthesized (C60)n nanochains with thiol spacers interspersed between the chains are achieved and visualized by scanning tunneling microscopic imaging under RT. This innovative integration of the vdW interaction unveils new avenues for developing supramolecular patterns characterized by their comparatively weak but exceptionally adaptable bonding. [ABSTRACT FROM AUTHOR]

The construction of a suitable stopper on a C60 orifice is of importance to prevent the release of once‐encapsulated chemical species. However, a single stopper on a large orifice is in usual not sufficient to retain a small molecule within the C60 cavity. In this work, we introduced a double stopper, constituted of two hydroxy groups, on a huge orifice with a ring‐atom count of 18 by a reduction using BH3⋅THF. The resulting double stopper was demonstrated to effectively isolate an argon atom inside the cavity so that the argon was retained even under mass spectrometric conditions at 200 °C. The structure of the open‐cage C60 derivative with the double stopper was confirmed by X‐ray diffraction analysis, showing a dimeric configuration via intermolecular hydrogen‐bondings. The dimerization behavior was also studied in solution. [ABSTRACT FROM AUTHOR]

The paper studies methane heating based on the magnetocaloric effect of fullerene C60. The theoretical description is based on the dynamics of a free classical particle. The mathematical model is proposed for the dynamics of the system consisting of fullerene C60 and methane molecules. The interaction between the system elements is described by the Lennard–Jones potential. The average temperature of the system is determined herein. Time dependences are suggested for the system temperatures. The fourth-order Runge-Kutta scheme is used to solve equations of motion. [ABSTRACT FROM AUTHOR]

The whimsical Las Vegas/Monte Carlo cubic dice are generalized to construct the combinatorial problem of enumerating all n-dimensional hypercube dice and dice of other shapes that exhibit cubic, icosahedral, and higher symmetries. By utilizing powerful generating function techniques for various irreducible representations, we derive the combinatorial enumerations of all possible dice in n-dimensional space with hyperoctahedral symmetries. Likewise, a number of shapes that exhibit icosahedral symmetries such as a truncated dodecahedron and a truncated icosahedron are considered for the combinatorial problem of dice enumerations with the corresponding shapes. We consider several dice with cubic symmetries such as the truncated octahedron, dodecahedron, and Rubik’s cube shapes. It is shown that all enumerated dice are chiral, and we provide the counts of chiral pairs of dice in the n-dimensional space. During the combinatorial enumeration, it was discovered that two different shapes of dice exist with the same chiral pair count culminating to the novel concept of isochiral polyhedra. The combinatorial problem of dice enumeration is generalized to multi-coloring partitions. Applications to chirality in n-dimension, molecular clusters, zeolites, mesoporous materials, cryptography, and biology are also pointed out. Applications to the nonlinear n-dimensional hypercube and other dicey encryptions are exemplified with romantic, clandestine messages: “I love U” and “V Elope at 2”.

The C60 fullerene molecule has attracted tremendous interest for its distinctive nearly spherical structure. By contrast, all-metal counterparts have been elusive: Fullerene-like clusters composed of noncarbon elements typically suffer from instability, resulting in more compact geometries that require multiple embedded atoms or external ligands for stabilization. In this work, we present the synthesis of an all-metal fullerene cluster, [K@Au12Sb20]5−, using a wet-chemistry method. The cluster's structure was determined by single crystal x-ray diffraction, which revealed a fullerene framework consisting of 20 antimony atoms. Theoretical calculations further indicate that this distinct cluster exhibits aromatic behavior. [ABSTRACT FROM AUTHOR]

Supramolecular chemistry is a multidisciplinary research area mostly associated with the investigation of host–guest interactions within intricate three-dimensional (3D) molecular architectures held together reversibly by various non-covalent interactions. Continuous efforts to develop such kinds of complex host–guest systems with designer oligopyrrolic macrocyclic receptors are a rapidly growing research domain, which is deeply involved in applied supramolecular chemistry research. These host–guest supramolecular complexes can be constructed by combining suitable electron-rich oligopyrrolic donors (as a host) with complementary electron-poor guests (as acceptors), held together by the ionic force of attraction triggered by intermolecular charge/electron transfer (CT/ET) transitions. Some of these resulting CT/ET ensembles are potential candidates for the construction of efficient optoelectronic materials, optical sensors, molecular switches, etc. In this Feature Article we aim to focus on these supramolecular ensembles composed by size and shape complementary electroactive oligopyrrolic molecular containers, which are suitable for spherical guest (e.g., buckminsterfullerene) complexation. We also provide a "state-of-the-art" overview on plausible applications of these particular host–guest systems. Our aim is to cover only specific electron-rich tetrathiafulvalene (TTF)-based oligopyrrolic receptors, e.g., TTF-calix[4]pyrroles, TTF-cryptands, TTF-porphyrins and exTTF-porphyrin-based molecular motifs reported to date, along with a brief outlining of their "functional behaviour" in materials chemistry research. [ABSTRACT FROM AUTHOR]

The first coordination‐saturated buckyball with a C60 molecule totally encased in an icosidodecahedral Cu30 in a (μ30‐(η2)30)‐fashion, namely C60@Cu30@Cl36N12, has been successfully realized by a C60‐templated assembly. The 48 outmost coordinating atoms (36Cl+12N) comprise a new simple polyhedron that is described by a ccf topology. Charge transfer from (CuI, Cl) to C60 explains the expansion of the light absorption up to 700 nm, and accounts for an ultrafast photophysical process that underpins its high photothermal conversion efficiency. This work makes a giant step forward in exohedral metallofullerene (ExMF) chemistry. [ABSTRACT FROM AUTHOR]

We present the synthesis of a new type of an expanded porphyrinoid macrocycle with a saddle‐shaped morphology and its complexation of C60 guest molecules. The new macrocycle contains four carbazole and four triazole moieties and can be readily synthesized via a copper‐catalyzed click reaction. It shows specific photo‐physical properties including fluorescence with a high quantum yield of 60 %. The combination of the saddle‐shaped geometry with the expanded π‐system allows for host–guest interactions with C60 in a stacked polymer fashion. Evidence for the presence of a host–guest complex is provided both in solution by NMR spectroscopy and in the solid state by X‐ray structure analysis. [ABSTRACT FROM AUTHOR]

We present the synthesis of a new type of an expanded porphyrinoid macrocycle with a saddle‐shaped morphology and its complexation of C60 guest molecules. The new macrocycle contains four carbazole and four triazole moieties and can be readily synthesized via a copper‐catalyzed click reaction. It shows specific photo‐physical properties including fluorescence with a high quantum yield of 60 %. The combination of the saddle‐shaped geometry with the expanded π‐system allows for host–guest interactions with C60 in a stacked polymer fashion. Evidence for the presence of a host–guest complex is provided both in solution by NMR spectroscopy and in the solid state by X‐ray structure analysis. [ABSTRACT FROM AUTHOR]

Fragments of buckminsterfullerene (C60) include the monumental three compounds corannulene, sumanene, and truxene. These three have served as leading molecules in ongoing research for curved, fused, and π‐extended polyaromatic materials. Achieving more structural variations that join the ranks of these three archetypes remains challenging. Herein we report synthesis of an octacyclic hydrocarbon that is an unexplored C60‐fragment, namely, a 4,11‐dihydrodiindeno[7,1,2‐ghi:7′,1′,2′‐pqr]chrysene (C28H16, which we named Metelykene). The key to success was solution‐compatible synthesis in which double pentagonal rings flank hexagonal ones. This solution‐phase approach, coupled with the resulting non‐planar π‐conjugation, is so straightforward that it offers an entry to a derivative such as a cardo aromatic monomer. [ABSTRACT FROM AUTHOR]

Perovskite Solar Cells (PSCs) have managed to significantly capture attention by achieving efficiency values of 25.6% in a remarkably short period of around ten years. Each layer within the device plays a crucial role in the overall device efficiency when it comes to PSC production. PC61BM, a derivative of fullerene, is one of the most commonly used electrontransport layers (ETLs) in inverted-type PSCs. In this study, the improvement of the ETL was aimed by incorporating C60 into PC61BM, and the effects of the doped ETL on MAPbI3-based inverted-type PSCs were investigated. For inverted type PSCs which are fabricated under high humidity (40-60%) and room conditions (~25 °C), the power conversion efficiencies (PCEs) have boosted from 11.54% (for undoped PC61BM) to 13.40% (for C60-doped PC61BM). To comprehend the sources of improvement in the fabricated devices, a series of characterizations were carried out, including Current Density-Voltage (J-V), Hysteresis Factor (HF), Scanning Electron Microscope (SEM), and Atomic Force Microscope (AFM) measurements. [ABSTRACT FROM AUTHOR]

Structure vis-à-vis the stability of mono- and poly-atomic buckminsterfullerene (C 60 ) complexes are capable of providing intrigue information about these systems. To obtain an insight of these complexes, geometrical parameters of fullerene encapsulated noble gas elements (He, Ne and Ar) and poly-atomic molecules (H 2 , H 2 O, NH 3 and CH 4 ) are computed at the restricted Hartree-Fock (RHF) as well as density functional (DFT) at the Becke, 3-parameter, Lee-Yang-Parr (B3LYP) level of theories. Ellipticity values estimated from mean maximal and mean minimal diameters of these endohedrals are found to be ∼ 0.2 which indicate that these complexes are of spheroidal shape. It is further observed that the fullerene ring is resilient to deformation and the structural parameters of these systems depend more on the method than the embedded system. Binding energies of these complexes are computed at the RHF, DFT, second order Möller-Plesset perturbation (MP2), spin-component scaled (SCS) MP2 and coupled-cluster with single and double excitation (CCSD) level of theories to assess electron correlation effects on the stability of these endohedrals. Resulted energies from the RHF procedure are found to be positive (energetically unstable), whereas those yielded by MP2 and SCS-MP2 procedures predict these endohedrals to be stable. CCSD calculations also exhibit similar trend except for H 2 O complex. Binding energies obtained using RHF, MP2, SCS-MP2 and CCSD procedures with correlation consistent polarized basis indicate a strong correlation between the basis set and the stability of these endohedral complexes. [ABSTRACT FROM AUTHOR]

Atomistic modeling of energy and charge transfer at the heterojunction of organic solar cells is an active field with many remaining outstanding questions owing, in part, to the difficulties in performing reliable photodynamics calculations on very large systems. One approach to being able to overcome these difficulties is to design and apply an appropriate simplified method. Density-functional tight binding (DFTB) has become a popular form of approximate density-functional theory based on a minimal valence basis set and neglect of all but two center integrals. We report the results of our tests of a recent long-range correction (lc) [A. Humeniuk and R. Mitrić, J. Chem. Phys. 143, 134120 (2015)] for time-dependent (TD) lc-DFTB by carrying out TD-lc-DFTB fewest switches surface hopping calculations of energy and charge transfer times using the relatively new DFTBABY [A. Humeniuk and R. Mitrić, Comput. Phys. Commun. 221, 174 (2017)] program. An advantage of this method is the ability to run enough trajectories to get meaningful ensemble averages. Our interest in the present work is less in determining exact energy and charge transfer rates than in understanding how the results of these calculations vary with the value of the range-separation parameter (Rlc = 1/μ) for a model organic solar cell heterojunction consisting of a gas-phase van der Waals complex P/F made up of a single pentacene (P) molecule together with a single buckminsterfullerene (F) molecule. The default value of Rlc = 3.03 a0 is found to be much too small as neither energy nor charge transfer is observed until Rlc ≈ 10 a0. Tests at a single geometry show that the best agreement with high-quality ab initio spectra is obtained in the limit of no lc (i.e., very large Rlc). A plot of energy and charge transfer rates as a function of Rlc is provided, which suggests that a value of Rlc ≈ 15 a0 yields the typical literature (condensed-phase) charge transfer time of about 100 fs. However, energy and charge transfer times become as high as ∼300 fs for Rlc ≈ 25 a0. A closer examination of the charge transfer process P*/F → P+/F− shows that the initial electron transfer is accompanied by a partial delocalization of the P hole onto F, which then relocalizes back onto P, consistent with a polaron-like picture in which the nuclei relax to stabilize the resultant redistribution of charges. [ABSTRACT FROM AUTHOR]

We present a method for efficient calculation of intramolecular vibrational excitations of H2O inside C60, together with the low-energy intermolecular translation-rotation states within each intramolecular vibrational manifold. Apart from assuming rigid C60, this nine-dimensional (9D) quantum treatment is fully coupled. Following the recently introduced approach [P. M. Felker and Z. Bačić, J. Chem. Phys. 151, 024305 (2019)], the full 9D vibrational Hamiltonian of H2O@C60 is partitioned into two reduced-dimension Hamiltonians, a 6D one for the intermolecular vibrations and another in 3D for the intramolecular degrees of freedom, and a 9D remainder term. The two reduced-dimension Hamiltonians are diagonalized, and their eigenvectors are used to build up a product contracted basis in which the full vibrational Hamiltonian is diagonalized. The efficiency of this methodology derives from the insight of our earlier study referenced above that converged high-energy intramolecular vibrational excitations of weakly bound molecular complexes can be obtained from fully coupled quantum calculations where the full-dimensional product contracted basis includes only a small number of intermolecular vibrational eigenstates spanning the range of energies much below those of the intramolecular vibrational states of interest. In this study, the eigenstates included in the 6D intermolecular contacted basis extend to only 410 cm−1 above the ground state, which is much less than the H2O stretch and bend fundamentals, at ≈3700 and ≈1600 cm−1, respectively. The 9D calculations predict that the fundamentals of all three intramolecular modes, as well as the bend overtone, of the caged H2O are blueshifted relative to those of the gas-phase H2O, the two stretch modes much more so than the bend. Excitation of the bend mode affects the energies of the low-lying H2O rotational states significantly more than exciting either of the stretching modes. The center-of-mass translational fundamental is virtually unaffected by the excitation of any of the intramolecular vibrational modes. Further progress hinges on the experimental measurement of the vibrational frequency shifts in H2O@C60 and ab initio calculation of a high-quality 9D potential energy surface for this endohedral complex, neither of which is presently available. [ABSTRACT FROM AUTHOR]

Isotopically enriched (3.5% 13C) and depleted (0.5% 13C) fullerene C60 molecules are isolated in parahydrogen (pH2) solids at cryogenic temperatures and studied by high resolution (0.01–0.1 cm−1) infrared (IR) absorption measurements. Spectra of natural isotopic abundance (1.1% 13C) C60 molecules isolated in solid pH2, orthodeuterium (oD2), and Ne matrix hosts serve to identify the relatively minor spectral perturbations due to the trapping environments. Spectral features observed for the four IR-active T1u modes of threefold degeneracy in Ih symmetry, namely, T1u(1) at 529.77 cm−1, T1u(2) at 578.24 cm−1, T1u(3) at 1184.7 cm−1, and T1u(4) at 1432 cm−1, are assigned to the superpositions of matrix perturbed vibrational-mode spectra of a number of 13Cn12C60−n isotopologues. New molecular orbital calculations show the symmetry lowering effects of 13C substitution, namely, split vibrational frequencies and modified IR intensities. IR spectral patterns calculated for the 328 distinct isotopomers of 13Cn12C60−n up to n = 3 are used to satisfactorily simulate most of the observed absorption features. For the T1u(4) mode at 1432 cm−1, the observed splitting is insensitive to the 13C abundance, indicating spectral perturbations due to Fermi resonance. Weak absorption features at 1545 cm−1 are assigned to a combination of lower frequency modes. We discuss relative and absolute band strengths for the astrophysical application of estimating C60 abundances in planetary nebulae. [ABSTRACT FROM AUTHOR]

Two metallofullerene frameworks (MFFs) constructed from a penta‐shell Keplerate cuprofullerene chloride, C60@Cu24@Cl44@Cu12@Cl12, have been successfully prepared via a C60‐templated symmetry‐driven strategy. The icosahedral cuprofullerene chloride is assembled on a C60 molecule through [η2‐(C=C)]−CuI and CuI−Cl coordination bonds, resulting in the penta‐shell Keplerate with the C60 core canopied by 24 Cu, 44 Cl, 12 Cu and 12 Cl atoms that fulfill the tic@rco@oae@ico@ico penta‐shell polyhedral configuration. By sharing the outmost‐shell Cl atoms, the cuprofullerene chlorides are connected into 2D or 3D (snf net) frameworks. TD‐DFT calculations reveal that the charge transfer from the outmost CuI and Cl to C60 core is responsible for their light absorption expansion to near‐infrared region, implying anionic halogenation may be an effective strategy to tune the light absorption properties of metallofullerene materials. [ABSTRACT FROM AUTHOR]

Carbon nano‐onions (CNOs) as a novel form of carbon materials hold peculiar structural features but their electrocatalytic applications are largely discouraged by the demanding synthesis conditions (e.g., ≥1500 °C and vacuum). Using C60 fullerene molecules as the sacrificial seeds and melamine as the main feedstock, herein, a novel strategy for the facile construction of CNOs nanoparticles is presented with ultrafine sizes (≈5 nm) at relatively low temperatures (≤900 °C) and atmospheric pressure. During the calcination, in‐depth characterizations reveal that C60 can retain the melamine‐derived graphitic carbon nitride from complete sublimation at high temperatures (≥700 °C). Owing to the N removal and subsequent pentagon generation, severely deformed graphitic fragments together with the disintegrated C60 molecules merge into larger sized nanosheets with high curvature, eventually leading to the formation of N‐doped defect‐rich CNOs. Owing to the integration of multiple favorable structural features of pentagons, edges, and N dopants, the CNOs obtained at 900 °C present superior oxygen reduction half‐wave potential (0.853 VRHE) and zinc–air cathode performance to the commercial Pt/C (0.838 VRHE). Density functional theory calculation further uncovers that the carbon atoms adjacent to the N‐doped edged pentagons are turned into the ORR‐active sites with O2 protonation as the rate‐determining step. [ABSTRACT FROM AUTHOR]

The iconic caged shape of fullerenes gives rise to a series of unique chemical and physical properties; hence a deeper understanding of the attractive and repulsive forces between two buckyballs can bring detrimental information about the structural stability of such complexes, providing significant data applicable for several studies. The potential energy curves for the interaction of multiple van der Waals buckyball complexes with increasing mass were theoretically obtained within the DFT framework at ωB97xD/6−31G(d) compound model. These potential energy curves were employed to estimate the spectroscopic constants and the lifetime of the fullerene complexes with the Discrete Variable Representation and with the Dunham approaches. It was revealed that both methods are compatible in determining the rovibrational structure of the dimers and that they are genuinely stable, i.e., long-lived complexes. To further inquire into the nature of such interaction, Bader's QTAIM approach was applied. QTAIM descriptors indicate that the interactions of these closed-shell systems are dominated by weak van der Waals forces. This non-covalent interaction character was confirmed by the RDG analysis scheme. Indirectly, QTAIM also allowed us to confirm the stability of the non-covalent bonded fullerene dimers. Our lifetime calculations have shown that the studied dimers are stable for more than 1 ps, which increases accordingly with the number of carbon atoms. [ABSTRACT FROM AUTHOR]

We have developed a highly efficient computation method based on density functional theory (DFT) within a set of fully symmetrized basis functions for the C60 buckyball, which possesses the icosahedral ( I h ) point-group symmetry with 120 symmetry operations. We demonstrate that our approach is much more efficient than the conventional approach based on three-dimensional plane waves. When applied to the calculation of optical transitions, our method is more than one order of magnitude faster than the existing DFT package with a conventional plane-wave basis. This makes it very convenient for modeling optical and transport properties of quantum devices related to buckyball crystals. The method introduced here can be easily extended to other fullerene-like materials. [ABSTRACT FROM AUTHOR]

The authors report on the behavior of C60 molecules adsorbed on graphene (Gr) monolayers grown on Rh(110), studied by means of scanning tunneling microscopy and spectroscopy under ultra‐high vacuum conditions. Fullerene molecules form a well‐ordered close packed hexagonal layout with an intermolecular distance of ≈1 nm. As demonstrated from the experimental data, the molecular packing direction of C60 is locally close to being aligned with the quasi‐1D moiré patterns formed by graphene on the metal support. Moreover, for certain orientations of graphene on Rh(110), the underlying moiré pattern appears superimposed on the molecular assembly. However, the analysis of the highest occupied molecular orbital and the lowest unoccupied molecular orbital structures and the differential conductance curves of C60 on Gr/Rh(110) suggest a weak molecule–substrate interaction, similar to other 2D material/metal interfaces. All these observations can imply that the moiré structures of Gr/Rh(110) play a central role in the arrangement of C60, but without modifying its electronic properties, which makes this Gr/Rh(110) system a singular platform for C60 adsorption. Complementarily, the structural properties of multilayer growth of C60 on Gr/Rh(110) are also investigated. [ABSTRACT FROM AUTHOR]

The thermodynamics of fullerene C60 in a magnetic field is examined. A theoretical description based on the classical particle dynamics models is used. The angular velocity of the fullerene in the magnetic field is found. An analogue of a gas thermometer is used to determine the temperature, with helium as the filling gas for the thermometer. The magnetocaloric effect of the fullerene is investigated. [ABSTRACT FROM AUTHOR]

Graphene has great potential in the field of solid lubricity due to its superlow friction and high wear resistance. However, the excellent tribological performance of graphene is degraded when it conformally contacts with a rough substrate. This work proposes a novel method to improve the tribological performance of graphene on a rough Si/SiO 2 substrate by filling grooves on the substrate surface with C60 molecules. When C60 filling is not performed, the friction force on the graphene surface increases rapidly at the groove edges where graphene presents large out-of-plane deformation due to its conformal contact with the substrate. Inspiringly, such high friction force is reduced by one order of magnitude when C60 filling is introduced to provide out-of-plane support to graphene for preventing its conformal contact with the substrate. Meanwhile, the high mechanical strength of C60 molecules enables a greater than 5-fold strengthening of the load-carrying capacity of graphene, which greatly improves its wear resistance on the rough substrate. These observations are helpful in promoting the tribological application of graphene by diminishing its conformal contact with the rough substrate. [Display omitted] [ABSTRACT FROM AUTHOR]

Nanobowls represent vital molecular building blocks of end-capped nanotubes and fullerenes detected in combustion systems and in deep space such as toward the planetary nebula TC-1, but their fundamental formation mechanisms have remained elusive. By merging molecular beam experiments with electronic structure calculations, we reveal a complex chain of reactions initiated through the gas-phase preparation of benzocorannulene (C24H12) via ring annulation of the corannulenyl radical (C20H9•) by vinylacetylene (C4H4) as identified isomer-selectively in situ via photoionization efficiency curves and photoion mass-selected threshold photoelectron spectra. In silico studies provided compelling evidence that the benzannulation mechanism can be expanded to pentabenzocorannulene (C40H20) followed by successive cyclodehydrogenation to the C40 nanobowl (C40H10) – a fundamental building block of buckminsterfullerene (C60). This high-temperature pathway opens up isomer-selective routes to nanobowls via resonantly stabilized free-radical intermediates and ring annulation in circumstellar envelopes of carbon stars and planetary nebulae as their descendants eventually altering our insights of the complex chemistry of carbon in our Galaxy. Nanobowls represent building blocks of fullerenes and nanotubes as detected in combustion systems and deep space, but their formation mechanisms in these environments have remained elusive. Here, the authors explore the gas-phase formation of benzocorannulene and beyond to the C40 nanobowl. [ABSTRACT FROM AUTHOR]

The removal of heavy metals from the environment has attracted considerable attention as they are toxic and non-biodegradable or destroyable. To minimize their hazard, they should be removed through either physical or chemical capture. Cadmium is a heavy metal that can lead to severe risks to human health. Using the density functional theory with a dispersion correction (DFT + D), we predict the structures and energies of Cd trapped by C60. Furthermore, we substitutionally doped C60 with a single B, Si, and N and examined its trapping behavior. The lowest substitutional energy was calculated for B. Significant enhancement in trapping is observed with B and Si doping outside the surface in particular and our results warrant further experimental investigation. [ABSTRACT FROM AUTHOR]

The removal of heavy metals from the environment has attracted considerable attention as they are toxic and non-biodegradable or destroyable. To minimize their hazard, they should be removed through either physical or chemical capture. Cadmium is a heavy metal that can lead to severe risks to human health. Using the density functional theory with a dispersion correction (DFT + D), we predict the structures and energies of Cd trapped by C60. Furthermore, we substitutionally doped C60 with a single B, Si, and N and examined its trapping behavior. The lowest substitutional energy was calculated for B. Significant enhancement in trapping is observed with B and Si doping outside the surface in particular and our results warrant further experimental investigation. [ABSTRACT FROM AUTHOR]

Three derivatives of macrocyclic cage compounds consisting of diarylanthracene and triptycene units were synthesized. These nanocages formed host‐guest complexes with C60 and other fullerene guests as confirmed by 1H NMR and fluorescence spectroscopy. The association constant of the mesityl and 2,4,6‐tributoxyphenyl derivatives with C60 was determined to be 2.2 × 104 L mol−1, which was larger than that of the pentafluorophenyl derivative. Direct experimental evidence of the complexation was obtained by X‐ray diffraction analysis: the guest C60 molecule was included in the cavity via multipoint CH⋅⋅⋅π interactions. Dynamic disorders of the included C60 molecule in variable‐temperature X‐ray analysis indicated uniaxial motion, such as gyroscopic motion. The unique dynamic behavior of the spherical C60 rotor anchored by the cage stator via CH⋅⋅⋅π interactions in the crystal, as well as substituent effects on the association properties, are discussed with the aid of DFT calculations. [ABSTRACT FROM AUTHOR]

Simultaneously enhancing the gas permeability, selectivity and aging stability of carbon molecular sieve membrane (CMSM) is extremely difficult. Facing such poser, a novel silicon doped CMSM at molecular level was prepared by copolymerizing siloxane with single Si– O –Si unit into the backbone of polyimide (PI). This can effectively avoid prior separated structure or multiple Si– O –Si structures and strongly alter the chains packing and thermostability of PI, finally determine the pore structure and thermodynamic behavior. The simple design adjustment simultaneously exhibits the triple enhanced effects on the gas permeability, selectivity and aging stability. The best molecule doped CMSM exhibits the ultra-high H 2 permeability (12482 Barrer, 87% higher), 26% higher H 2 /CH 4 selectivity, and 32% higher H 2 /N 2 selectivity than pure PI based CMSM. Additionally, such CMSM also has a much better aging stability than pure CMSM and most reported CMSMs. After stabilization, it still maintains a high H 2 permeability (8000 Barrer). And the hyper-aging CMSM also exhibits a good aging resistance showing a H 2 permeability of 5300 Barrer, as well as high selectivity of H 2 /CH 4 (125) and H 2 /N 2 (106) after 35 days. This work opens a new way on designing CMSM with excellent performance through heteroatom doping to need future application. [Display omitted] • A novel molecule doping of silicon in CMSMs was achieved. • The addition of siloxane affects the packing and decomposition of PI chains. • Both gas permeability and selectivity of CMSMs were improved. • The silicon doped CMSM exhibited excellent aging stability. • The aged CMSM maintains a high H 2 permeability of 8000 Barrer. [ABSTRACT FROM AUTHOR]

Endohedral metallofullerenes (EMFs) are excellent carriers of rare‐earth element (REE) ions in biomedical applications because they preclude the release of toxic metal ions. However, existing approaches to synthesize water‐soluble EMF derivatives yield mixtures that inhibit precise drug design. Here we report the synthesis of metallobuckytrio (MBT), a three‐buckyball system, as a modular platform to develop structurally defined water‐soluble EMF derivatives with ligands by choice. Demonstrated with PEG ligands, the resulting water‐soluble MBTs show superb biocompatibility. The Gd MBTs exhibit superior T1 relaxivity than typical Gd complexes, potentially superseding current clinical MRI contrast agents in both safety and efficiency. The Lu MBTs generated reactive oxygen species upon light irradiation, showing promise as photosensitizers. With their modular nature to incorporate other ligands, we anticipate the MBT platform to open new paths towards bio‐specific REE drugs. [ABSTRACT FROM AUTHOR]

The epitaxial growth of metallic thin films has been studied intensively, leading to computational models that can predict diverse morphologies depending on thermodynamic and kinetic growth parameters. Much less is known about thin films of organic molecules. Here kinetic Monte Carlo simulations to study buckyball C60 molecules on dielectric CaF2(111) substrates is employed. This system undergoes a transition from mostly one‐layered growth to two‐layered growth of triangular cluster morphologies as the temperature is raised. Even though simplified, these simulations still require a large set of parametrized rates for the elementary transitions, the determination of which has been challenging. Here recent results for these parameters to measure cluster densities and second layer occupations are employed. Simulation snapshots of cluster morphologies are compared in a wide range of temperatures to test to which extent rate models can match the experimental observations. While adjustments to free diffusion parameters are necessary to reproduce the experimentally observed cluster densities and sizes, the cluster morphologies are excellently reproduced without further adjustments. [ABSTRACT FROM AUTHOR]

The Eu@C60(OH)30 and Eu@C60(OH)20endo-structures were predicted by the (U)DFT quantum chemical method. The arrangement of hydroxyl groups corresponds to the arrangement of chlorine atoms in (D3d)-C60Cl30 and fluorine atoms in (D5d)-C60F20. The calculated squares of the electron spin ‹Ŝ2› were reproduced with high accuracy by the addition of the spins belonging to two unpaired valence electrons and 4f7 subsystem. The total spin multiplicity of the quasi-degenerate ground state is 2·2·8. Some of its 32 components can be distinguished by the IR spectrum. The europium avoids benzoid cycles. It is located asymmetrically within the [18]trannulene cycle in the Eu@C60(OH)30 complex and between a peripheral carbon atoms of the corannulene fragments in the Eu@C60(OH)20 complex. The value ‹Ŝ2› ≈ 16.75 a. u., calculated with MS = 7/2, is key number. It allows limiting the DFT study to only one spin component out of 32 possible components. In contrast with Eu@C60(OH)30 and Eu@C60(OH)20, the Eu@C60 has two quasi-degenerate endohedral spin-tautomers. The (C3v) tautomer includes the hexagonal pyramid EuC6 formed as a result of endohedral η6-bonding of the europium with cyclohexa-1,3,5-triene fragment of buckminsterfullerene. It was obtained for the low-spin and high-spin components of the quasi-degenerate state with the total multiplicity 3·8. The (C2v) tautomer includes a triangular EuC2 fragment and was obtained for the octet spin state. The energy difference of the spin-tautomers is small, but the difference in its IR spectra is very large. [ABSTRACT FROM AUTHOR]

[Display omitted] • Unique buckyball ligands identified for binding to BACE1 active site. • Thirteen BACE1 residues crucial for binding to buckyball ligands. • New mode of interaction with key and previously underappreciated BACE1 residues. • FEP revealed 4_C26_d3hc demonstrating the greatest potential. Alzheimer's disease, marked by cognitive decline and memory loss, involves BACE1 in generating Aβ peptides, making it a key drug target. This study screened 129 buckyball ligands using molecular docking, identifying three promising compounds (4_C26_d3hc, 8_C20_Ih, and 16_C24_d6d) that fit within the BACE1 binding site. Molecular dynamics simulations highlighted thirteen BACE1 residues crucial for binding to buckyball ligands. The binding affinities of these ligands were also revealed via free energy perturbation (FEP), with 4_C26_d3hc demonstrating the greatest potential. This work lays the foundation for developing new BACE1 inhibitors using buckyball structures, offering a promising approach for Alzheimer's therapy. [ABSTRACT FROM AUTHOR]

Graph theory (GT) serves as a mathematical foundation that helps us to manipulate, develop, analyze, and comprehend the chemical networks or structures and their characteristics. Molecular graph is a graph made up of vertices (atoms) and edges (chemical bonds between atoms). Chemical GT applied geometrical and combinatorial GT to model the important chemical structures of chemistry. Chemical GT has a wide range of uses in the study of chemical structures. The examination and manipulation of chemical structural information is made feasible by utilizing the numerical graph invariants. A graph invariant or a topological index (TI) is a numerical measure of a chemical compound that is capable of describing the properties of chemical compounds, such as melting point, freezing point, density, pressure, tension, and temperature. In this article, we compute connection-based Zagreb indices (CBZIs), namely first CBZI, second CBZI, modified first CBZI, modified second CBZI, and modified third CBZI for one of the significant types of molecular structure named as crystal cubic carbon structure, which is the most important allotrope of carbon atom. Moreover, to examine the superiority and authenticity of our computed TIs, we compare the calculated values of these ZIs for crystal cubic carbon structure with each other. This comparison enables us to check which CBZI is more authentic and superior to predict the physical and chemical properties of crystal cubic carbon structure. [ABSTRACT FROM AUTHOR]

We present the construction of a M2L4‐type metal‐organic nanocage featuring four endohedral Feringa's motor motifs and its adaptive encapsulation towards a C60 guest molecule. The structure of the cage, though complicated on the 1H NMR spectrum due to the adoption of mixed ligands, was unambiguously characterized with a combination of ESI‐MS, 2D DOSY, 13C NMR and particularly the SAXS technique. The molecular motor within the cage demonstrated similar photophysical properties to the uncoordinated one, indicating the motor's function was not compromised when it was anchored in such a confined nanospace. Furthermore, the nanocage showed good guest encapsulation ability towards C60, and a guest induced‐fit behavior of the cage was revealed based on the extensive SAXS analysis and molecular dynamics simulation. The adaptive motorized nanocage reported here represents one of the very few examples of integrating individual motors into a discrete nanoconfined system and offers prospects to achieve its non‐equilibrium functions. [ABSTRACT FROM AUTHOR]