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- ItemExpansion of the (BB)Ru metallacycle with coinage metal cations: Formation of B-M-Ru-B (M = Cu, Ag, Au) dimetalacyclodiboryls(Cambridge : Royal Society of Chemistry, 2018) Eleazer, B.J.; Smith, M.D.; Popov, A.A.; Peryshkov, D.V.In this work, we introduce a novel approach for the selective assembly of heterometallic complexes by unprecedented coordination of coinage metal cations to strained single ruthenium-boron bonds on a surface of icosahedral boron clusters. M(i) cations (M = Cu, Ag, and Au) insert into B-Ru bonds of the (BB)-carboryne complex of ruthenium with the formation of four-membered B-M-Ru-B metalacycles. Results of theoretical calculations suggest that bonding within these metalacycles can be best described as unusual three-center-two-electron B-M⋯Ru interactions that are isolobal to B-H⋯Ru borane coordination for M = Cu and Ag, or the pairs of two-center-two electron B-Au and Au-Ru interactions for M = Au. These transformations comprise the first synthetic route to exohedral coinage metal boryl complexes of icosahedral closo-{C2B10} clusters, which feature short Cu-B (2.029(2) Å) and Ag-B (2.182(3) Å) bonds and the shortest Au-B bond (2.027(2) Å) reported to date. The reported heterometallic complexes contain Cu(i) and Au(i) centers in uncharacteristic square-planar coordination environments. These findings pave the way to rational construction of a broader class of multimetallic architectures featuring M-B bonds.
- ItemMetallofullerene photoswitches driven by photoinduced fullerene-to-metal electron transfer(Cambridge : RSC, 2021) Zalibera, Michal; Ziegs, Frank; Schiemenz, Sandra; Dubrovin, Vasilii; Lubitz, Wolfgang; Savitsky, Anton; Deng, Shihu H.M.; Wang, Xue-Bin; Advoshenko, Stanislav M.; Popov, Alexey A.We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of YxSc3−xN@C80 (x = 0–3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S1–T1 gap decrease in this row. For Sc3N@C80, we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin–lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14N, 45Sc, and 89Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y3N to Sc3N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.
- ItemProcessing metallic glasses by selective laser melting(Amsterdam [u.a.] : Elsevier, 2013) Pauly, S.; Löber, L.; Petters, R.; Stoica, M.; Scudino, S.; Kühn, U.; Eckert, J.Metallic glasses and their descendants, the so-called bulk metallic glasses (BMGs), can be regarded as frozen liquids with a high resistance to crystallization. The lack of a conventional structure turns them into a material exhibiting near-theoretical strength, low Young's modulus and large elasticity. These unique mechanical properties can be only obtained when the metallic melts are rapidly cooled to bypass the nucleation and growth of crystals. Most of the commonly known and used processing routes, such as casting, melt spinning or gas atomization, have intrinsic limitations regarding the complexity and dimensions of the geometries. Here, it is shown that selective laser melting (SLM), which is usually used to process conventional metallic alloys and polymers, can be applied to implement complex geometries and components from an Fe-base metallic glass. This approach is in principle viable for a large variety of metallic alloys and paves the way for the novel synthesis of materials and the development of parts with advanced functional and structural properties without limitations in size and intricacy.
- Item(BB)-Carboryne Complex of Ruthenium: Synthesis by Double B-H Activation at a Single Metal Center(Washington, DC : ACS Publications, 2016) Eleazer, Bennett J.; Smith, Mark D.; Popov, Alexey A.; Peryshkov, Dmitry V.The first example of a transition metal (BB)-carboryne complex containing two boron atoms of the icosahedral cage connected to a single exohedral metal center (POBBOP)Ru(CO)2 (POBBOP = 1,7-OP(i-Pr)2-2,6-dehydro-m-carborane) was synthesized by double B-H activation within the strained m-carboranyl pincer framework. Theoretical calculations revealed that the unique three-membered (BB)>Ru metalacycle is formed by two bent B-Ru σ-bonds with the concomitant increase of the bond order between the two metalated boron atoms. The reactivity of the highly strained electron-rich (BB)-carboryne fragment with small molecules was probed by reactions with electrophiles. The carboryne-carboranyl transformations reported herein represent a new mode of cooperative metal-ligand reactivity of boron-based complexes.
- ItemHigh-defect hydrophilic carbon cuboids anchored with Co/CoO nanoparticles as highly efficient and ultra-stable lithium-ion battery anodes(Cambridge : Royal Society of Chemistry, 2016) Sun, Xiaolei; Hao, Guang-Ping; Lu, Xueyi; Xi, Lixia; Liu, Bo; Si, Wenping; Ma, Chuansheng; Liu, Qiming; Zhang, Qiang; Kaskel, Stefan; Schmidt, Oliver G.We propose an effective strategy to engineer a unique kind of porous carbon cuboid with tightly anchored cobalt/cobalt oxide nanoparticles (PCC–CoOx) that exhibit outstanding electrochemical performance for many key aspects of lithium-ion battery electrodes. The host carbon cuboid features an ultra-polar surface reflected by its high hydrophilicity and rich surface defects due to high heteroatom doping (N-/O-doping both higher than 10 atom%) as well as hierarchical pore systems. We loaded the porous carbon cuboid with cobalt/cobalt oxide nanoparticles through an impregnation process followed by calcination treatment. The resulting PCC–CoOx anode exhibits superior rate capability (195 mA h g−1 at 20 A g−1) and excellent cycling stability (580 mA h g−1 after 2000 cycles at 1 A g−1 with only 0.0067% capacity loss per cycle). Impressively, even after an ultra-long cycle life exceeding 10 000 cycles at 5 A g−1, the battery can recover to 1050 mA h g−1 at 0.1 A g−1, perhaps the best performance demonstrated so far for lithium storage in cobalt oxide-based electrodes. This study provides a new perspective to engineer long-life, high-power metal oxide-based electrodes for lithium-ion batteries through controlling the surface chemistry of carbon host materials.
- ItemSelf-assembly of endohedral metallofullerenes: A decisive role of cooling gas and metal-carbon bonding(Cambridge : Royal Society of Chemistry, 2016) Deng, Qingming; Heine, Thomas; Irle, Stephan; Popov, Alexey A.The endohedral metallofullerene (EMF) self-assembly process in Sc/carbon vapor in the presence and absence of an inert cooling gas (helium) is systematically investigated using quantum chemical molecular dynamics simulations. It is revealed that the presence of He atoms accelerates the formation of pentagons and hexagons and reduces the size of the self-assembled carbon cages in comparison with analogous He-free simulations. As a result, the Sc/C/He system simulations produce a larger number of successful trajectories (i.e. leading to Sc-EMFs) with more realistic cage-size distribution than simulations of the Sc/C system. The main Sc encapsulation mechanism involves nucleation of several hexagons and pentagons with Sc atoms already at the early stages of carbon vapor condensation. In such proto-cages, both Sc–C σ-bonds and coordination bonds between Sc atoms and the π-system of the carbon network are present. Sc atoms are thus rather labile and can move along the carbon network, but the overall bonding is sufficiently strong to prevent dissociation even at temperatures around 2000 kelvin. Further growth of the fullerene cage results in the encapsulation of one or two Sc atoms within the fullerene. In agreement with experimental studies, an extension of the simulations to Fe and Ti as the metal component showed that Fe-EMFs are not formed at all, whereas Ti is prone to form Ti-EMFs with small cage sizes, including Ti@C28-Td and Ti@C30-C2v(3).
- ItemTunable charge transfer properties in metal-phthalocyanine heterojunctions(Cambridge : Royal Society of Chemistry, 2016) Siles, P.F.; Hahn, T.; Salvan, G.; Knupfer, M.; Zhu, F.; Zahn, D.R.T.; Schmidt, O.G.Organic materials such as phthalocyanine-based systems present a great potential for organic device applications due to the possibility of integrating films of different organic materials to create organic heterostructures which combine the electrical capabilities of each material. This opens the possibility to precisely engineer and tune new electrical properties. In particular, similar transition metal phthalocyanines demonstrate hybridization and charge transfer properties which could lead to interesting physical phenomena. Although, when considering device dimensions, a better understanding and control of the tuning of the transport properties still remain in the focus of research. Here, by employing conductive atomic force microscopy techniques, we provide an insight about the nanoscale electrical properties and transport mechanisms of MnPc and fluorinated phthalocyanines such as F16CuPc and F16CoPc. We report a transition from typical diode-like transport mechanisms for pure MnPc thin films to space-charge-limited current transport regime (SCLC) for Pc-based heterostructures. The controlled addition of fluorinated phthalocyanine also provides highly uniform and symmetric-polarized transport characteristics with conductance enhancements up to two orders of magnitude depending on the polarization. We present a method to spatially map the mobility of the MnPc/F16CuPc structures with a nanoscale resolution and provide theoretical calculations to support our experimental findings. This well-controlled nanoscale tuning of the electrical properties for metal transition phthalocyanine junctions stands as key step for future phthalocyanine-based electronic devices, where the low dimension charge transfer, mediated by transition metal atoms could be intrinsically linked to a transfer of magnetic moment or spin.
- ItemMixed dysprosium-lanthanide nitride clusterfullerenes DyM2N@C80-: I h and Dy2MN@C80- i h (M = Gd, Er, Tm, and Lu): Synthesis, molecular structure, and quantum motion of the endohedral nitrogen atom(Cambridge : RSC Publ., 2019) Schlesier, C.; Liu, F.; Dubrovin, V.; Spree, L.; Büchner, B.; Avdoshenko, S.M.; Popov, A.A.Systematic exploration of the synthesis of mixed-metal Dy-M nitride clusterfullerenes (NCFs, M = Gd, Er, Tm, Lu) is performed, and the impact of the second metal on the relative yield is evaluated. We demonstrate that the ionic radius of the metal appears to be the main factor allowing explanation of the relative yields in Dy-M mixed-metal systems with M = Sc, Lu, Er, and Gd. At the same time, Dy-Tm NCFs show anomalously low yields, which is not consistent with the relatively small ionic radius of Tm3+ but can be explained by the high third ionization potential of Tm. Complete separation of Dy-Gd and Dy-Er, as well as partial separation of Dy-Lu M3N@C80 nitride clusterfullerenes, is accomplished by recycling HPLC. The molecular structures of DyGd2N@C80 and DyEr2N@C80 are analyzed by means of single-crystal X-ray diffraction. A remarkable ordering of mixed-metal nitride clusters is found despite similar size and electronic properties of the metals. Possible pyramidalization of the nitride clusters in these and other nitride clusterfullerenes is critically analyzed with the help of DFT calculations and reconstruction of the nitrogen inversion barrier in M3N@C80 molecules is performed. Although a double-well potential with a pyramidal cluster structure is found to be common for most of them, the small size of the inversion barrier often leads to an apparent planar structure of the cluster. This situation is found for those M3N@C80 molecules in which the energy of the lowest vibrational level exceeds that of the inversion barrier, including Dy3N@C80 and DyEr2N@C80. The genuine pyramidal structure can be observed by X-ray diffraction only when the lowest vibrational level is below the inversion barrier, such as those found in Gd3N@C80 and DyGd2N@C80. The quantum nature of molecular vibrations becomes especially apparent when the size of the inversion barrier is comparable to the energy of the lowest vibrational levels.
- ItemRotation of fullerene molecules in the crystal lattice of fullerene/porphyrin: C60 and Sc3N@C80(Cambridge : RSC, 2021) Hao, Yajuan; Wang, Yaofeng; Spree, Lukas; Liu, FupinThe dynamics of molecules in the solid-state is important to understand their physicochemical properties. The temperature-dependent dynamics of Sc3N@C80 and C60 in the crystal lattice containing nickel octaethylporphyrin (NiOEP) was studied with variable temperature X-ray diffraction (VT-XRD). The results indicate that the fullerene cages (both C60 and C80) in the crystal lattice present stronger libration than the co-crystallized NiOEP in the temperature range of 100–280 K. In contrast to the fullerene cage, the Sc3N cluster shows pronounced rotation roughly perpendicular to the plane of the co-crystallized NiOEP molecule driven by temperature. The obtained temperature dependent dynamic behavior of the Sc3N cluster is different from that of Ho2LuN and Lu3N, regardless of their rather similar structure, indicating the effect of the mass and size of the metal ions.