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Surface cracks could improve the optical and photoelectronic properties of crystalline materials as they increase specific surface area, but the controlled self-assembly of fullerene (C60 ) molecules into micro-/nanostructures with surface cracks is still challenging. Herein, we report the morphology engineering of novel C60 microstructures bearing surface cracks for the first time, selecting phenetole and propan-1-ol (NPA) as good and poor solvents, respectively. Our systematic investigations reveal that phenetole molecules initially participate in the formation of the ends of the C60 microstructures, and then NPA molecules are involved in the gradual growth of the sidewalls of the microstructures. Therefore, the surface cracks of C60 microstructures can be finely regulated by adjusting the addition of NPA and the crystallization time. Interestingly, the cracked C60 microstructures show superior photoluminescence properties relative to the smooth microstructures due to the increased specific surface area. In addition, C60 microstructures with wide cracks show preferential recognition of silica particles over C60 particles owing to electrostatic interactions between the negatively charged C60 microstructures and the positively charged silica microparticles. These C60 crystals with surface cracks have potential applications from optoelectronics to biology.

With respect to molecular switches, initializing the quadricyclane (QC) to norbornadiene (NBD) back‐reaction by light is highly desirable. Our previous publication provided a unique solution for this purpose by utilizing covalently bound C60. In this work, the fundamental processes within these hybrids has been investigated. Variation of the linker unit connecting the NBD/QC moiety with the fullerene core is used as a tool to tune the properties of the resulting hybrids. Utilizing the Prato reaction, two unprecedented NBD/QC – fullerene hybrids having a long‐rigid and a short‐rigid linker were synthesized. Molecular dynamics simulations revealed that this results in an average QC–C60 distance of up to 14.2 Å. By comparing the NBD–QC switching of these derivatives with the already established one having a flexible linker, valuable mechanistic insights were gained. Most importantly, spatial convergence of the QC moiety and the fullerene core is inevitable for an efficient back‐reaction., Spatial distance has a major impact on the photoswitching in NBD/QC – fullerene hybrids. By careful molecular design and using MD simulations it was possible to gain valuable insight into the mechanism underlying these unique photoswitches.

Reactions of Pd8 strings supported by meso-Ph2 PCH2 P(Ph)CH2 P(Ph)CH2 PPh2 (meso-dpmppm) ligands, [Pd8 (meso-dpmppm)4 (L)2 ]4+ (L=CH3 CN (1), XylNC (2)) with C60 resulted in the exclusive formation of unprecedented metal-chain-wired C60 bucky balls, [{Pd4 (meso-dpmppm)2 (L)}2 (C60 )]4+ (L=CH3 CN (11), XylNC (12)), in which a C60 fullerene is trapped in the central Pd-Pd junction, as unambiguously established by spectroscopic, X-ray crystallographic, and theoretical techniques. The similar reaction of Pd8 strings supported by rac-dpmppm, [Pd8 (rac-dpmppm)4 (CH3 CN)2 ]4+ (3) also afforded a racemic mixture of [{Pd4 ((R*,R*)-dpmppm)2 (CH3 CN)}2 (C60 )]4+ (13) without scrambling the Pd4 fragments with (R,R)- and (S,S)-dpmppm ligands. Consequently, those of enantiopure chiral Pd8 strings, [Pd8 ((R*,R*)-dpmppm)4 (CH3 CN)2 ]4+ , certainly afforded chiral bucky balls of [{Pd4 ((R*,R*)-dpmppm)2 (CH3 CN)}2 (C60 )]4+ (13RR and 13SS ), that exhibit mirror-image circular dichroism spectra. The reactions of 1 and 2 were also applied for trapping a C70 fullerene to give 2 : 1 adducts of [{Pd4 (meso-dpmppm)2 (L)}2 (C70 )]4+ (L=CH3 CN (21), XylNC (22)). These results provide useful information for creating a platform to develop dimensionally and chirality controlled metal-carbon nanocomposite materials.

Controlled crystallization of fullerene molecules into ordered molecular assemblies is important for their applications. However, the morphology engineering of fullerene[C70 ] assemblies is challenging, and complicated architectures have rarely been reported due to the low molecular symmetry of C70 molecules, which makes their crystallization difficult to control and the low production yield as well. Herein, with the assistance of solvent intercalation, a general reprecipitation approach is reported to prepare morphologically controllable C70 microcrystals with mesitylene as a good solvent and n-propanol as a poor solvent in one solvent system without replacing specific solvents. A series of C70 microcrystals with high uniformity from perfect cubes and defective hoppers to novel cruciform-pillars are obtained by intentionally tuning C70 concentration and the volume ratio of mesitylene to n-propanol. Among them, novel cruciform-pillar-shaped microcrystals are obtained for the first time by further decreasing the amount of mesitylene in the solvent-intercalated microcrystals. Notably, the C70 concentration is a key parameter for the selective growth of C70 hopper, rather than the volume ratio of mesitylene to n-propanol. Interestingly, the hopper-shaped microcrystals exhibit excellent photoluminescence properties relative to those of cubes and cruciform-pillars owing to the enhanced light absorption, proving their potential applications in optoelectronic devices. This study offers new insights into the morphology-controlled synthesis of other micro/nanostructured organic microcrystals and the fine tuning of photoluminescence properties of organic crystals.

Cage-opened bisfulleroids are one of suitable building blocks for making a large hole on fullerenes. This work focuses on the Diels-Alder reaction of C60 with azines, among synthetic methods developed thus far, to provide bisfulleroids. Surprisingly, the computational study predicted that the reaction proceeds with normal electron demand in contrast to hitherto considered inverse-electron-demand pathway. The benzoannulation to the pyridazine ring, i. e., phthalazine, resulted in the remarkably shortened reaction time due to the better interaction between the HOMO of phthalazine and the LUMO of C60 as well as stronger 2,3-diaza-1,3-butadiene character in the phthalazine as confirmed crystallographically. Contrary to expectations, the benzobisfulleroid was converted into corresponding orifice-enlarged derivative via the photooxygenation slightly faster than the fulleroid derived from pyridazine.

By nucleophilic addition of phosphite P(OMe)3 to a cage-opened C60 derivative, α-hydrophosphate and enol phosphate were obtained as kinetic and thermodynamic products, respectively. Different from classical Abramov products bearing a phosphorus-carbon bond, these products have a phosphorus-oxygen bond. The observed anomaly originates from the fully conjugated π system, which significantly stabilizes zwitterionic intermediates bearing a phosphorus-oxygen bond. The thus formed enol phosphate was found to exhibit an intense absorption band that extended to 730 nm, reflecting the intramolecular charge-transfer transitions. We also report domino phosphorylation reactions, which gave a cage-opened C60 derivative bearing a direct P-C bond.

The carriers of the diffuse interstellar bands (DIBs) are still largely unknown although polycyclic aromatic hydrocarbons, carbon chains, and fullerenes are likely candidates. A recent analysis of the properties of n‐acenes of general formula C4n+2H2n+4 suggested that these could be potential carriers of some DIBs. Dehydrogenation reactions of n‐acenes after absorption of an interstellar UV photon may result in dehydroacenes. Here the reaction energies and barriers for formation of n‐cyclacenes from 2,3‐didehydroacenes (n‐DDA) by intramolecular Diels–Alder reaction to dihydro‐etheno‐cyclacenes (n‐DEC) followed by ejection of ethyne by retro‐Diels–Alder reactions are analyzed using thermally assisted occupation density functional theory (TAO‐DFT) for n=10–20. It is found that the barriers for each of the steps depend on the ring strain of the underlying n‐cyclacene, and that the ring strain of n‐DEC is about 75 % of that of the corresponding n‐cyclacene. In each case, ethyne extrusion is the step with the highest energy barrier, but these barriers are smaller than CH bond dissociation energies, suggesting that formation of cyclacenes is an energetically conceivable fate of n‐acenes after multiple absorption of UV photons., n ‐Acenes (C4n+2H2n+4) are potential carrier candidates for diffuse interstellar bands. Their conversion into n‐cyclacenes (C4nH2n) through UV photon‐initiated dehydrogenation followed by Diels–Alder cycloaddition and acetylene expulsion appears energetically plausible. Analysis of the conversion through TAO‐DFT reveals dependency of the energy barriers on ring strains of the primary n‐cyclacene.

The development of highly efficient metal-free electrocatalysts for the oxygen reduction reaction (ORR) has attracted great attention for the creation of electrochemical energy devices. In this study, one-dimensional (1 D) fullerene nanofibers prepared from liquid-liquid interfacial precipitation are first fabricated into fullerene-derived carbon nanofiber films (FCNFs) through a simple filtration procedure. Then, pyrolysis of the FCNFs in the presence of ammonia and sulfur produces N- and S-co-doped porous carbon nanofiber films (N,S-PCNFs). As excellent metal-free electrocatalysts for the ORR, N,S-PCNFs exhibit remarkable catalytic activity, superior stability, and excellent methanol tolerance in both alkaline and acidic solution. Such a high ORR performance benefits from the robust porous nanofiber network structure with high concentrations of active N- and S- groups and abundant defects. Notably, upon practical use of N,S-PCNFs as catalysts in Zn-air batteries, a high power density and a large operating voltage are achieved, with a performance comparable to that of the commercial Pt/C catalyst. This work presents a facile strategy for the creation of a new class of energy nanomaterials based on fullerenes, demonstrating their practical uses in electrocatalytic ORR processes and Zn-air batteries.

The single-crystal micro/nanostructures of fullerene species, namely C60 and C70 , have been previously studied, but studies on the morphology and properties of higher fullerenes have rarely been reported due to the limited amount of samples and their ellipsoidal isomeric structures. Herein, we report the formation of three-dimensional (3D) micro-cubes and micro-dice of a higher fullerene (C78 ) via a facile liquid-liquid interfacial precipitation (LLIP) method. The micro-cubes were prepared by regulating the concentration of C78 in trimethylbenzene (TMB) and the volume ratio of TMB and isopropanol. Interestingly, the micro-cubes are transformed into micro-dice with an open-hole on each crystal face by simply shaking the solution. X-ray diffraction and Fourier-transform infrared spectroscopic studies revealed a simple cubic unit cell with a lattice constant of 10.6 A and intercalated TMB molecules in both crystals. The C78 cubic and dice-like microstructures exhibited enhanced photoelectrochemical and photoluminescence properties compared with pristine C78 powder, indicating their potential applications as photodetectors and photoelectric devices.

In the last 30 years, fullerene-based materials have become popular building blocks for devices with a broad range of applications. Among fullerene derivatives, endohedral metallofullerenes (EMFs, M@Cx) have been widely studied owing to their unique properties and reactivity. For real applications, fullerenes and EMFs must be exohedrally functionalized. It has been shown that encapsulated metal cations facilitate the Diels-Alder reaction in fullerenes. Herein, the Bingel-Hirsch (BH) addition of ethyl bromomalonate over a series of ion-encapsulated M@C60 (M=O, Li+, Na+, K+, Mg2+, Ca2+, and Cl-; O@C60 stands for C60 without any endohedral metal) is quantum mechanically explored to analyze the effect of these ions on the BH addition. The results show that the incarcerated ion has a very important effect on the kinetics and thermodynamics of this reaction. Among the systems studied, K+@C60 is the one that leads to the fastest BH reaction, whereas the slowest reaction is given by Cl-@C60.

The extension of fused aromatic ring core structures is beneficial for enhancing intramolecular charge transfer and effective π conjugation in A-D-A-type (A=acceptor; D=donor) non-fullerene acceptors (NFAs). In this work, a novel strategy involving the extension of a fused-ring core by symmetrically replicating the core unit has been developed, and a novel symmetric fused-12-ring NFA, LC81, has been synthesized. When paired with the wide-bandgap polymer donor PBT1-C, the corresponding organic solar cells (OSCs) showed a high power conversion efficiency of 12.71 %, much higher than that of the device based on the reference NFA, TPTT-4F. Moreover, the LC81-based OSC displayed a lower energy loss and a better ambient stability than the TPTT-4F-based device. Our results indicate that the extension of the fused-ring core by the symmetric replicating core unit strategy is an effective approach to promoting the photovoltaic characteristics of A-D-A-type NFAs.

Porous carbon materials rich in defects are promising candidates in energy storage and conversion applications. Herein, a facile template-free approach is reported for the synthesis of a two-dimensional (2 D) mesoporous carbon material derived from fullerene (C60 ) microsheets (FMSs) through simple heat treatment. The sample obtained at 1000 °C (FMS1000) shows a large surface area of 1507.6 m2 g-1 owing to the presence of mesopores and rich defects, which promote electron and mass transfer in the electrocatalytic process of the oxygen reduction reaction (ORR), showing an excellent performance with an onset potential of 0.95 V, a half-wave potential of 0.85 V, and long-term durability of 2000 cycles, comparable to the performance of commercial Pt/C. Moreover, FMS1000 displays a remarkable supercapacitive property with a specific capacitance of 330.7 F g-1 at 0.2 A g-1 and good long-term stability with a capacitance retention of 97 % over 50 000 cycles. Thus, a practical strategy for the production of mesoporous carbon materials with different morphological structures and porous defects as high-performance energy materials is advanced.

A mechanistic study on the distinct hydrogen evolution reactivity (HER) of three cyclometalated IrIII complex���polyoxometalate (Ir���POMM) dyads. Their HER activity was tuned by modifying the central metal ion M of the POMM. The lifetime or the yield of Ir.+���POMM.��� determined the different HER activity of Ir���POMM (see figure). Covalently linked photosensitizer���polyoxometalate (PS���POM) dyads are promising molecular systems for light���induced energy conversion processes, such as ���solar��� hydrogen generation. To date, very little is known of their fundamental photophysical properties which affect the catalytic reactivity and stability of the systems. PS���POM dyads often feature short���lived photoinduced charge���separated states, and the lifetimes of these states are considered crucial for the function of PS���POM dyads in molecular photocatalysis. Hence, strategies have been developed to extend the lifetimes of the photoinduced charge���separated states, either by tuning the PS photophysics or by tuning the POM redox properties. Recently, some of us reported PS���POM dyads based on cyclometalated IrIII complexes covalently linked to Anderson���type polyoxometalate. Distinct hydrogen evolution reactivity (HER) of the dyads was observed, which was tuned by varying the central metal ion M of the POMM (M=Mn3+, Co3+, Fe3+). In this manuscript, the photoinduced electron���transfer processes in the three Ir���POMM dyads are investigated to rationalize the underlying reasons for the differences in HER activity observed. We report that upon excitation of the IrIII complex, ultrafast (sub���ps) charge separation occurs, leading to different amounts of the charge���separated states (Ir.+���POMM.���) generated in the different dyads. However, in all dyads studied, the resulting Ir.+���POMM.��� species are short���lived (sub���ns) when compared to reference electron acceptors (e.g. porphyrins or fullerenes) reported in the literature. The reductive quenching of Ir.+���POMM.��� by a sacrificial donor, triethyl amine (1 m), to generate the intermediate Ir���POMM.��� is estimated to be very efficient (70���80 %) for all dyads studied. Based on this analyses, we conclude that the yield instead of the lifetime of the Ir.+���POMM.��� charge���separated state determines the catalytic capacity of the dyads investigated. This new feature in the PS���POM photophysics could lead to new design criteria for the development of novel PS���POM dyads., publishedVersion

A multimodular donor-acceptor conjugate featuring silicon phthalocyanine (SiPc) as the electron donor, and two electron acceptors, namely tetrachloroperylenediimide (PDI) and C60 , placed at the opposite ends of the SiPc axial positions, was newly designed and synthesized, and the results were compared to the earlier reported PDI-SiPc-C60 triad. Minimal intramolecular interactions between the entities was observed. Absorption, fluorescence, computational and electrochemical studies were performed to evaluate the excitation energy, geometry and electronic structure, and energy levels of different photoevents. Steady-state absorption, fluorescence and excitation spectral studies revealed efficient singlet-singlet energy transfer from 1 PDI* to SiPc in the PDI-SiPc dyad and the PDI-SiPc-C60 triad. The measured rates for these photochemical events were found to be much higher than those reported earlier for the triad, due to closer proximity between the PDI and SiPc entities. The distance also affected the charge separation path in which involvement of PDI, and not C60 , in charge separation in the present triad was witnessed. The present investigation brings out the importance of donor-acceptor distances in channeling photochemical events in a multimodular system.

Endohedral metallofullerenes (EMFs), namely fullerenes with metallic species encapsulated inside, represent an ideal platform to investigate metal-metal or metal-carbon interactions at the sub-nanometer scale by means of single-crystal X-ray diffraction (XRD) crystallography. Herein, recent progress in the identification of new structures and unprecedented properties are discussed according to the categories of monometallofullerenes, dimetallofullerenes, carbide clusterfullerenes, and nitride clusterfullerenes. In particular, the dimerization and the cage-isomer dependent oxidation state of the inner metal atom are summarized in terms of pristine monometallofullerenes. Metal-metal bonds involving lanthanide-lanthanides or actinide-actinides are discussed based on both experimental and theoretical studies. The cluster-cage matching and/or mutual selections, as well as the rarely seen M=C double bonds, are discovered in M2 C2 @C2n , U2 C@C80 , M2 TiC@C80 , and Ti3 C3 @C80 . Subsequently, the geometries of different M3 N clusters in various cages are discussed, revealing size-matching between the internal M3 N cluster and the outer cage induced by the planarity of the cluster. Finally, an outlook regarding the future developments of the molecular structures and applications of EMFs is presented.

The carbon cage of buckminsterfullerene Ih -C60 , which obeys the Isolated-Pentagon Rule (IPR), can be transformed to non-IPR cages in the course of high-temperature chlorination of C60 or C60 Cl30 with SbCl5 . The non-IPR chloro derivatives were isolated chromatographically (HPLC) and characterized crystallographically as 1809 C60 Cl16 , 1810 C60 Cl24 , and 1805 C60 Cl24 , which contain, respectively two, four, and four pairs of fused pentagons in the carbon cage. High-temperature trifluoromethylation of the chlorination products with CF3 I afforded a non-IPR CF3 derivative, 1807 C60 (CF3 )12 , which contains four pairs of fused pentagons in the carbon cage. Addition patterns of non-IPR chloro and CF3 derivatives were compared and discussed in terms of the formation of stabilizing local substructures on fullerene cages. A detailed scheme of the experimentally confirmed non-IPR C60 isomers obtained by Stone-Wales cage transformations is presented.

Chemical modification of endohedral metallofullerenes (EMFs) is an efficient strategy to realize their ultimate applications in many fields. Herein, we report the highly regioselective and quantitative mono-formation of pyrazole- and pyrrole-ring-fused derivatives of the prototypical di-EMF Y2 @C3v (8)-C82 , that is, Y2 @C3v (8)-C82 (C13 N2 H10 ) and Y2 @C3v (8)-C82 (C9 NH11 ), from the respective 1,3-dipolar reactions with either diphenylnitrilimine or N-benzylazomethine ylide, without the formation of any bis- or multi-adducts. Crystallographic results unambiguously reveal that only one [6,6]-bond out of the twenty-five different types of nonequivalent C-C bonds of Y2 @C3v (8)-C82 is involved in the 1,3-dipolar reactions. Our theoretical results rationalize that the remarkably high regioselectivity and the quantitative formation of mono-adducts are direct results from the anisotropic distribution of π-electron density on the C3v (8)-C82 cage and the local strain of the cage carbon atoms as well. Interestingly, electrochemical and theoretical studies demonstrate that the reversibility of the redox processes, in particular the reversibility of the reductive processes of Y2 @C3v (8)-C82 , has been markedly altered upon exohedral functionalization, but the oxidative process was less influenced, indicating that the oxidation is mainly influenced by the internal Y2 cluster, whereas the reduction is primarily associated with the fullerene cage. The pyrazole and pyrrole-fused derivatives may find potential applications as organic photovoltaic materials and biological reagents.

Data concerning the isomeric composition of C98 and the chemistry of C98 derivatives are scarce due to very low abundance of C98 in the fullerene soot. Trifluoromethylation of C98 -containing mixtures followed by HPLC separation of CF3 derivatives and single crystal X-ray diffraction study resulted in structural characterization of four compounds C98 (248)(CF3 )18/20 , C98 (116)(CF3 )18 , and C98 (120)(CF3 )20 . To date, these compounds represent the largest fullerenes isolated as CF3 derivatives with experimentally determined molecular structures. The addition patterns of C98 (CF3 )18/20 are discussed in detail revealing the stabilizing factors, such as isolated double C=C bonds and benzenoid rings on C98 fullerene cages. A detailed comparison with the addition patterns of the known C98 Cln allowed us to contribute to the better understanding the chemistry of elusive C98 fullerene.

Discovery of permanent magnetisation in molecules just like in hard magnets decades ago led to the proposal of utilising these molecules for information storage devices and also as Q-bits in quantum computing. A significant breakthrough with a blocking temperature as high as 80 K has been recently reported for lanthanocene complexes. While enhancing the blocking temperature further remains one of the primary challenges, obtaining molecules that are suitable for the fabrication of the devices sets the bar very high in this area. Encouraged by the fact that our earlier predictions of potential single-molecule magnets (SMMs) in lanthanide-containing endohedral fullerenes have been verified, here we set out to undertake a comprehensive study on CoII -ion-encapsulated fullerene as potential SMMs. To study this class of molecules, we have utilised an array of theoretical methods ranging from density functional to ab initio CASSCF/NEVPT2 methods for obtaining reliable estimate of zero-field splitting parameters D and E. Additionally, we have also employed, for the first time a combination of molecular dynamics based on DFT methods coupled with CASSCF/NEVPT2 methods to seek the role of conformational isomers in the relaxation of magnetisation. Particularly, we have studied, Co@C28 , Co@C38 and Co@C48 cages and their isomers as potential target molecules that could yield substantial magnetic anisotropy. Our calculations categorically reveal a very large Ising anisotropy in this class of molecules, with Co@C48 cages predicted to yield D values as high as -127 cm-1 . Our calculations on the smaller cages reveal the free movement of CoII ion inside the cage, leading to the likely scenario of faster relaxation of magnetisation. However, larger fullerene cages were found to solve this issue. Further models with incorporating units such as {CoOZn}, {CoScZnN} inside larger fullerenes yield axial zero-field splitting values as high as -200 cm-1 with negligible E/D values. As these units represent a strong axiality coupled with a viable way to obtain air-stable low-coordinate CoII complexes, this opens up a new paradigm in the search of SMMs in this class of molecules.

Vibrational circular dichroism (VCD) studies are reported on a chiral compound in which a fullerene C60 moiety is used as an electron acceptor and local VCD amplifier for an alanine‐based peptide chain. Four redox states are investigated in this study, of which three are reduced species that possess low‐lying electronic states as confirmed by UV/Vis spectroelectrochemistry. VCD measurements in combination with (TD)DFT calculations are used to investigate (i) how the low‐lying electronic states of the reduced species modulate the amplification of VCD signals, (ii) how this amplification depends on the distance between oscillator and amplifier, and (iii) how the spatial extent of the amplifier influences amplification. These results pave the way for further development of tailored molecular VCD amplifiers., Amplifying the difference between left and right with a buckyball: C60 has been used to amplify vibrational circular dichroism signals. Switchable and tunable amplification is achieved by utilizing the various redox states of C60. DFT calculations on how vibrational motion influences the electronic distribution pave the way for further optimization of such “extended” amplifiers.

The modification of metal electrode surfaces with functional organic molecules is an important part of organic electronics. The interaction of the buckminsterfullerene fragment molecule pentaindenocorannulene with a Cu(100) surface is studied by scanning tunneling microscopy, dispersion-enabled density functional theory, and force field calculations. Experimental and theoretical methods suggest that two adjacent indeno groups become oriented parallel to the surface upon adsorption under mild distortion of the molecular frame. The binding mechanism between molecule and surface is dominated by strong electrostatic interaction owing to Pauli repulsion. Two-dimensional aggregation at room temperature leads to a single lattice structure in which all molecules are oriented unidirectionally. Their relative arrangement in the lattice suggests noncovalent intermolecular interaction through C-H⋅⋅⋅π bonding.

Purified samples of Ho3 N@C2 (22010)-C78 and Tb3 N@C2 (22010)-C78 have been isolated by two distinct processes from the rich array of fullerenes and endohedral fullerenes present in carbon soot from graphite rods doped with Ho2 O3 or Tb4 O7 . Crystallographic analysis of the endohedral fullerenes as cocrystals with Ni(OEP) (in which OEP is the dianion of octaethylporphyrin) shows that both molecules contain the chiral C2 (22010)-C78 cage. This cage does not obey the isolated pentagon rule (IPR) but has two sites where two pentagons share a common C-C bond. These pentalene units bind two of the metal ions, whereas the third metal resides near a hexagon of the cage. Inside the cages, the Ho3 N or Tb3 N unit is planar. Ho3 N@C2 (22010)-C78 and Tb3 N@C2 (22010)-C78 use the same cage previously found for Gd3 N@C2 (22010)-C78 rather than the IPR-obeying cage found in Sc3 N@D3h -C78 .

A first series of examples for confined space interactions of electron-rich and electron-poor molecules organized in an internal corona of shell-by-shell (SbS)-structured Al2 O3 nanoparticle (NP) hybrids is reported. The assembly concept of the corresponding hierarchical architectures relies on both covalent grafting of phosphonic acids on the NPs surface (SAMs formation; SAM=self-assembled monolayer) and exohedral interdigitation of orthogonal amphiphiles as the second ligand layer driven by solvophobic interactions. The electronic communication between the chromophores of different electron demand, such as pyrenes, perylenediimides (PDIs; with and without pyridinium bromide headgroups) and fullerenes was promoted at the layer interface. In this work, it is demonstrated that the efficient construction principle of the bilayer hybrids assembled around the electronically "innocent" Al2 O3 core is robust enough to achieve control over electronic communication between electron-donors and -acceptors in the interlayer region. The electronic interactions between the electron-accepting and electron-donating moieties approaching each other at the layer interface were monitored by fluorescence measurements.

A series of covalent ferrocene-BODIPY-fullerene triads with the ferrocene groups conjugated to the BODIPY π-system and the fullerene acceptor linked at the boron hub by a common catecholpyrrolidine bridge were prepared and characterized by 1D and 2D NMR, UV/Vis, steady-state fluorescence spectroscopy, high-resolution mass spectrometry, and, for one of the derivatives, X-ray crystallography. Redox processes of the new compounds were investigated by electrochemical (CV and DPV) methods and spectroelectrochemistry. DFT calculations indicate that the HOMO in all triads was delocalized between ferrocene and BODIPY π-system, the LUMO was always fullerene-centered, and the catechol-centered occupied orbital was close in energy to the HOMO. TDDFT calculations were indicative of the low-energy, low-intensity charge-transfer bands originated from the ferrocene-BODIPY core to fullerene excitation, which explained the similarity of the UV/Vis spectra of the ferrocene-BODIPY dyads and ferrocene-BODIPY-fullerene triads. Photophysical properties of the new triads as well as reference BODIPY-fullerene and ferrocene-BODIPY dyads were investigated by pump-probe spectroscopy in the UV/Vis and NIR spectral regions following selective excitation of the BODIPY-based antenna. Initial charge transfer from the ferrocene to the BODIPY core was shown to outcompete sub-100 fs deactivation of the excited state mediated by the catechol bridge. However, no subsequent electron transfer to the fullerene acceptor was observed. The initial charge separated state relaxes by recombination with a time constant of 150-380 ps.

A systematic screening study of the exohedral reactivity of the reduced fullerenes (fullerenides) C60 2- and C60 ⋅- is reported. These doubly and singly negatively charged carbon cages were prepared by two-fold reduction of C60 with potassium, leading to K2 C60 , or by in situ monoreduction with the radical anion of benzonitrile PhCN⋅- , respectively. Several series of electrophiles, including geminal and distant dihalides, benzyl bromides, and diazonium compounds, were employed as addition partners. In general, the investigated bromides proved to be the most suitable reaction partners. A series of fullerene adducts and cycloadducts involving either 1,2- or 1,4-addition patterns, depending on the precise architecture and the steric demand of the addends, were synthesized and fully characterized. Some of the reaction products are unprecedented and inaccessible forms of neutral C60 . The fullerenide chemistry presented here closely resembles related reactions of graphenides and carbon nanotubides, which are the most powerful methods for the functionalization of these macromolecular forms of synthetic carbon allotropes (SCAs). Activation of C60 by negative charging represents a little explored concept of fullerene chemistry, providing both new insights of fullerene reactivity itself and new types of exohedral derivatives.

A new cosensitization photoelectrochemical (PEC) strategy was established by using a donor-acceptor-type photoactive material, poly{4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophene-4,6-diyl} (PTB7-Th), as a signal indicator, which was cosensitized with bis(4,4'dicarboxyl-2,2'-bipyridyl)(4,5,9,14-tetraazabenzo[b]triphenylene)ruthenium(II) ([Ru(dcbpy)2 dppz]2+ ) embedded in the grooves of the DNA duplex and fullerene (nano-C60 ) immobilized on the surface of DNA nanoflowers for microRNA assay. [Ru(dcbpy)2 dppz]2+ and nano-C60 could effectively enhance the photoelectric conversion efficiency (PCE) of PTB7-Th as a result of well-matched energy levels among nano-C60 , [Ru(dcbpy)2 dppz]2+ and PTB7-Th, leading to a clearly enhanced photocurrent signal. Meanwhile, a target recycling magnification technique based on duplex-specific nuclease was applied in this work to obtain higher detection sensitivity. The proposed biosensor demonstrated excellent analytical properties within a linear detection range of 2.5 fm to 2.5 nm and a limit of detection down to 0.83 fm. Impressively, this cosensitization PEC strategy offers an effective and convenient avenue to significantly improve the PCE of a photoactive material, resulting in a remarkably improved photocurrent signal for ultrasensitive and highly accurate detection of various targets.