Electron interactions with the heteronuclear carbonyl precursor H₂FeRu₃(CO)₁₃ and comparison with HFeCo₃(CO)₁₂: from fundamental gas phase and surface science studies to focused electron beam induced deposition

• Ragesh Kumar T P,
• Paul Weirich,
• Lukas Hrachowina,
• Marc Hanefeld,
• Ragnar Bjornsson,
• Helgi Rafn Hrodmarsson,
• Sven Barth,
• D. Howard Fairbrother,
• Michael Huth and
• Oddur Ingólfsson

Beilstein J. Nanotechnol. 2018, 9, 555–579, doi:10.3762/bjnano.9.53

• framework of the metal atoms of these heterometallic clusters. In H2FeRu3(CO)13 and HFeCo3(CO)12 each tetrahedron contains one iron atom and three ruthenium or cobalt atoms, respectively. The coordination sphere contains the carbonyl as well as hydride ligands, which results in a highly symmetrical molecule

Influence of the preparation method on the photocatalytic activity of Nd-modified TiO₂

• Patrycja Parnicka,
• Paweł Mazierski,
• Tomasz Grzyb,
• Wojciech Lisowski,
• Ewa Kowalska,
• Bunsho Ohtani,
• Adriana Zaleska-Medynska and
• Joanna Nadolna

Beilstein J. Nanotechnol. 2018, 9, 447–459, doi:10.3762/bjnano.9.43

• cannot be effectively incorporated into the TiO2 lattice. Additionally, a full inclusion of Nd3+ ions may be hindered by the low coordination number of Ti4+ ions (CN = 6), because Nd3+ ions prefer sites with CN = 8 or 9. Therefore, it is reasonable to assume that Nd-containing species are localized at

Electron interaction with copper(II) carboxylate compounds

• Michal Lacko,
• Peter Papp,
• Iwona B. Szymańska,
• Edward Szłyk and
• Štefan Matejčík

Beilstein J. Nanotechnol. 2018, 9, 384–398, doi:10.3762/bjnano.9.38

• used to identify the fragmentation pattern of the coordination compounds produced in crossed electron – molecular beam experiments and to measure the dependence of ion yields of positive and negative ions on the electron energy. The dissociation pattern of positive ions contains a sequential loss of

• or coordination compounds suitable for FEBID. Previous gas phase studies performed in Bratislava with coordination compounds have shown the importance of DI and DEA processes in FEBID [10][11][12][17][18][19][35]. The partial decomposition of the metal complex via DI and DEA together with the role of

• be markedly different due to the absence of alkylamine ligands. As shown in Figure 3 and listed in Table 1, we have obtained for [Cu2(µ-O2CC2F5)4] appearance energies for sequential loss of carboxylate ligands. Usually, the dissociation of ligands from coordination compounds requires higher incident

Anchoring of a dye precursor on NiO(001) studied by non-contact atomic force microscopy

• Sara Freund,
• Antoine Hinaut,
• Nathalie Marinakis,
• Edwin C. Constable,
• Ernst Meyer,
• Catherine E. Housecroft and
• Thilo Glatzel

Beilstein J. Nanotechnol. 2018, 9, 242–249, doi:10.3762/bjnano.9.26

• ) changes to a cis-conformation upon coordination of a metal ion Mn+ (right). From large-scale imaging to atomic resolution on NiO(001). (a) Large scale topographic image of the NiO(001) crystal presenting clean terraces (scan parameters: = 4 nm, Δf1 = −30 Hz). The high-resolution topographic image (b

Response under low-energy electron irradiation of a thin film of a potential copper precursor for focused electron beam induced deposition (FEBID)

• Leo Sala,
• Iwona B. Szymańska,
• Céline Dablemont,
• Anne Lafosse and
• Lionel Amiaud

Beilstein J. Nanotechnol. 2018, 9, 57–65, doi:10.3762/bjnano.9.8

• ). Compound A and B exhibit very similar vibrational signatures. Ethylamine apical ligands are visible by the signatures of the ν(CH) stretching band 360–380 meV, and the ν(NH) stretching band, positioned in the 380–400 meV range due to the coordination by the nitrogen group [18]. Additional small signatures

• coordinated to Cu2+ cations. It would be interesting to investigate if the low lying shape resonance of π* character near 1 eV, involved in the dissociative electron attachment process on carboxylic acids, is preserved in a coordination complex and could lead to the cleavage of the Cu–OOCR coordination bond

The rational design of a Au(I) precursor for focused electron beam induced deposition

• Ali Marashdeh,
• Thiadrik Tiesma,
• Niels J. C. van Velzen,
• Sjoerd Harder,
• Remco W. A. Havenith,
• Jeff T. M. De Hosson and
• Willem F. van Dorp

Beilstein J. Nanotechnol. 2017, 8, 2753–2765, doi:10.3762/bjnano.8.274

• shows four short Au–Au bonds per Au atom and should, therefore, be regarded as being strongly bound by aurophilic interactions [71]. This can be attributed to the small size and needle-like coordination of the CO ligand. Figure 4 shows that ClAuCO crystallizes as a 2D polymeric structure. It seems that

Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers

• Xiaoli Sun and
• Zhiguo Wang

Beilstein J. Nanotechnol. 2017, 8, 2711–2718, doi:10.3762/bjnano.8.270

• views of ball and stick models of a MX2 monolayer in (a) 2H, (b) 1T and (c) 1T' phase. The M atoms have octahedral and trigonal prismatic coordination in the 1T/1T' and 2H phase, respectively. Band structures of MX2 monolayers in the stable phase. Fermi energy level is set to be 0. Possible adsorption

The role of ligands in coinage-metal nanoparticles for electronics

• Ioannis Kanelidis and
• Tobias Kraus

Beilstein J. Nanotechnol. 2017, 8, 2625–2639, doi:10.3762/bjnano.8.263

• ], CTAB [66][70], or oleylamine [87] are commonly used on metal particles and provide some colloidal stability; thicker polymer shells in good solvents generally lead to greater stability [88][89]. The ligands are anchored on the cores through metal–ligand coordination, hydrophobic adsorption or

Synthesis of [{AgO₂CCH₂OMe(PPh₃)}_n] and theoretical study of its use in focused electron beam induced deposition

• Jelena Tamuliene,
• Julian Noll,
• Peter Frenzel,
• Tobias Rüffer,
• Alexander Jakob,
• Bernhard Walfort and
• Heinrich Lang

Beilstein J. Nanotechnol. 2017, 8, 2615–2624, doi:10.3762/bjnano.8.262

• Chemnitz, Germany 10.3762/bjnano.8.262 Abstract The synthesis, chemical and physical properties of [{AgO2CCH2OMe}n] (1) and [{AgO2CCH2OMe(PPh3)}n] (2) are reported. Consecutive reaction of AgNO3 with HO2CCH2OMe gave 1, which upon treatment with PPh3 produced 2. Coordination compound 2 forms a 1D

• coordination polymer in the solid state as evidenced by single crystal X-ray structure analysis. The coordination geometry at Ag+ is of the [3 + 1] type, whereby the carboxylate anions act as bridging ligands. The formation of PPh3–Ag(I) coordinative bonds results in distorted T-shaped AgPO2 units, which are

• was shown that coordination compounds, for example, silver(I) carboxylates can successfully be applied as single-source species for silver nanoparticle formation [6] and as gas-phase precursors in the deposition of pure, dense and conformal thin silver films [7][8][9]. This study aims for showing if

Adsorption of iron tetraphenylporphyrin on (111) surfaces of coinage metals: a density functional theory study

• Hao Tang,
• Nathalie Tarrat,
• Véronique Langlais and
• Yongfeng Wang

Beilstein J. Nanotechnol. 2017, 8, 2484–2491, doi:10.3762/bjnano.8.248

• between these two stable magnetic states is essentially associated to the strength of the ligand field. The modification of the coordination sphere of the metallic centre is thus necessary to manipulate its spin state. Most of such manipulations have been achieved by coordinating an additional small

• molecule (e.g., NO, CO) or atom (Cl) in order to modify the coordination number [8][9][10][11]. Only few reversible manipulations of spin were achieved without additional ligand, as the one shown by N. Lin et al. on a single FeTPP molecule junction in a scanning tunnelling microscope (STM) [12]. In this

• . At the end, the relationship between the substrate and the coordination sphere of Fe is discussed in terms of molecule–surface interaction, charge transfer and work function modification. Results and Discussion Free molecule and conformations The ideal D4h symmetry, exhibiting the phenyl rings

Fabrication of CeO₂–MO_x (M = Cu, Co, Ni) composite yolk–shell nanospheres with enhanced catalytic properties for CO oxidation

• Ling Liu,
• Jingjing Shi,
• Hongxia Cao,
• Ruiyu Wang and
• Ziwu Liu

Beilstein J. Nanotechnol. 2017, 8, 2425–2437, doi:10.3762/bjnano.8.241

• general wet-chemical approach. It involved a non-equilibrium heat-treatment of Ce coordination polymer colloidal spheres (Ce-CPCSs) with a proper heating rate to produce CeO2 yolk–shell nanospheres, followed by a solvothermal treatment of as-synthesized CeO2 with M(CH3COO)2 in ethanol solution. During the

• integration of coordination chemistry with anti-solvent effects for synchronized precipitation. Second, the resultant Ce-CPCSs served as the precursor to produce CeO2 yolk–shell nanospheres by non-equilibrium heat treatment with a proper heating rate. Heterogeneous contraction, caused by non-equilibrium heat

Dissociative electron attachment to coordination complexes of chromium: chromium(0) hexacarbonyl and benzene-chromium(0) tricarbonyl

• Janina Kopyra,
• Paulina Maciejewska and
• Jelena Maljković

Beilstein J. Nanotechnol. 2017, 8, 2257–2263, doi:10.3762/bjnano.8.225

• [9], and HFeCo3(CO)12 [33], the bare metal ions were either not observed or observed with very low intensity (below 0.5% of the most intense anionic fragment). Conclusion In the present contribution, we have investigated how different ligands within coordination complexes modify the formation of

• , besides the direct decomposition of TNI, may also be generated via sequential, metastable decay. In the framework of the potential role of coordination complexes of chromium for FEBID applications, we note that the removal of C6H6 and all CO ligands to form exceptionally intense signal of bare [Cr]− has

The interplay between spin densities and magnetic superexchange interactions: case studies of mono- and trinuclear bis(oxamato)-type complexes

• Azar Aliabadi,
• Bernd Büchner,
• Vladislav Kataev and
• Tobias Rüffer

Beilstein J. Nanotechnol. 2017, 8, 2245–2256, doi:10.3762/bjnano.8.224

• double resonance; spin density distribution; Introduction The flexibility of carbon chemistry together with the structural variety of coordination chemistry offers unique possibilities to design new coordination complexes. This includes the potential of metalloligands for a metallosupramolecular

• related higher nuclear magnetic materials. There are already reports of spin and electron density distribution studies by polarized neutron and high-resolution X-ray diffraction measurements, respectively, for a ferrimagnetic type-IV coordination polymer [30][31]. Both studies revealed formidable direct

• shown to be sufficient for this purpose [9], since at Q- and especially at W-band frequencies the powder pattern of the ESR spectrum arising due to the g-factor anisotropy is much better resolved. We demonstrated that the higher the tetrahedral distortion of the CuN2O4 coordination units of type-II

Au₅₅, a stable glassy cluster: results of ab initio calculations

• Dieter Vollath,
• David Holec and
• Franz Dieter Fischer

Beilstein J. Nanotechnol. 2017, 8, 2221–2229, doi:10.3762/bjnano.8.222

• thermodynamically most stable structure is not crystalline, but it is glassy. The non-crystalline structure of this cluster was validated by comparison of the coordination numbers with those of a crystalline cluster. It was found that, in contrast to bulk materials, glass formation is connected to an energy release

• shells [1][4]. On average, these clusters are composed of 13 atoms in the center and 42 atoms in the outer shell. From the atoms in the outer shell, 18 atoms are bond to the ligands [1]. Furthermore, these shells show a very broad scattering of the coordination numbers [4]. This fact was taken as an

• al. [7], described the shape of the Au55 cluster as cuboctahedral. It must be mentioned that there are also findings, especially related to the coordination numbers, that the Au55 cluster is possibly structurally close to the face-centered cubic (fcc) structure [8][9][10]. Baletto and Ferrando prefer

Ta₂N₃ nanocrystals grown in Al₂O₃ thin layers

• Krešimir Salamon,
• Maja Buljan,
• Iva Šarić,
• Mladen Petravić and
• Sigrid Bernstorff

Beilstein J. Nanotechnol. 2017, 8, 2162–2170, doi:10.3762/bjnano.8.215

• understood through the influence of the Al2O3 component on the coordination and mobility of the tantalum atoms. Indeed, the tantalum nearest-neighbour distance in the as-grown films is relatively large, even 20% larger than that found in the amorphous Ta–N films obtained under high nitrogen fraction in

• sputtering gas mixture [16]. Such coordination of tantalum atoms presumably leads to the formation of a tantalum nitride phase with a lower density. It is important to note that the diffraction patterns for both MLs annealed at 900 °C are in fact the superposition of diffraction peaks and a broad maximum

Ester formation at the liquid–solid interface

• Nguyen T. N. Ha,
• Thiruvancheril G. Gopakumar,
• Nguyen D. C. Yen,
• Carola Mende,
• Lars Smykalla,
• Maik Schlesinger,
• Roy Buschbeck,
• Tobias Rüffer,
• Heinrich Lang,
• Michael Mehring and
• Michael Hietschold

Beilstein J. Nanotechnol. 2017, 8, 2139–2150, doi:10.3762/bjnano.8.213

• Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India Inorganic Chemistry, Institute of Chemistry, Technische Universität Chemnitz, D-09107 Chemnitz, Germany, Coordination Chemistry, Institute of Chemistry, Technische Universität Chemnitz, D-09107 Chemnitz, Germany 10.3762

Systematic control of α-Fe₂O₃ crystal growth direction for improved electrochemical performance of lithium-ion battery anodes

• Nan Shen,
• Miriam Keppeler,
• Barbara Stiaszny,
• Holger Hain,
• Filippo Maglia and
• Madhavi Srinivasan

Beilstein J. Nanotechnol. 2017, 8, 2032–2044, doi:10.3762/bjnano.8.204

• released into solution. Since it is understood that this coordination will specifically take place on the α-Fe2O3 surface facets with only singly coordinated hydroxyl groups, this interaction mechanism can be applied to direct the crystal growth in a specific growth direction. It was found that 1,2

• verified by results of our test series. Diamines are typical chelate ligands that interact with appropriate coordination centers. First, octahedral-shaped complexes are formed [29], formally described as (Fe[C2H2N2R1R2]3)3+. Diamine derivatives, in which the two amine groups are located at adjacent C atoms

Imidazolium-based ionic liquids used as additives in the nanolubrication of silicon surfaces

• Patrícia M. Amorim,
• Ana M. Ferraria,
• Rogério Colaço,
• Luís C. Branco and
• Benilde Saramago

Beilstein J. Nanotechnol. 2017, 8, 1961–1971, doi:10.3762/bjnano.8.197

• , it mainly hydrated the substrate surface. However, in both cases, ambient humidity was found to disturb the ion-pair coordination, which resulted in an increase in friction [31]. Tests carried out at macroscale showed the same effect when using hydrophobic imidazolium-based ILs to lubricate silica

Fluorination of vertically aligned carbon nanotubes: from CF₄ plasma chemistry to surface functionalization

• Claudia Struzzi,
• Mattia Scardamaglia,
• Jean-François Colomer,
• Alberto Verdini,
• Luca Floreano,
• Rony Snyders and
• Carla Bittencourt

Beilstein J. Nanotechnol. 2017, 8, 1723–1733, doi:10.3762/bjnano.8.173

• by the inelastic mean free path of the electrons and by the transmission function of the spectrometer analyser. The C 1s spectra are characterized by an intense peak associated to the C–C bond in sp2 coordination (located at 284.5 eV). For the functionalized samples, a shoulder appears at about 286

• eV accounting for an increased contribution of the C–C bond in sp3 coordination and for C atom first neighbour of fluorinated carbon atoms (as C–CF). In addition, new peaks emerge in the energy range going from 288 to 294 eV due to the covalent C–F bond formation, with contributions from covalent C–F

Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands

• Martin Börner,
• Laura Blömer,
• Marcus Kischel,
• Peter Richter,
• Georgeta Salvan,
• Dietrich R. T. Zahn,
• Pablo F. Siles,
• Maria E. N. Fuentes,
• Carlos C. B. Bufon,
• Daniel Grimm,
• Oliver G. Schmidt,
• Daniel Breite,
• Bernd Abel and
• Berthold Kersting

Beilstein J. Nanotechnol. 2017, 8, 1375–1387, doi:10.3762/bjnano.8.139

• , prevent the packing and self-assembly of the hydrocarbon chains. The smaller film thickness of 7 is attributed to the specific coordination mode of the coligand. Results of preliminary transport measurements utilizing rolled-up devices are also reported. Keywords: ambidentate ligands; chemisorption; gold

• , typical for an octahedral NiN3S2O carboxylate chromophore (assigned as ν2(3A2g→3T2g) and ν1(3A2g→3T1g), respectively, in pure Oh symmetry). Infrared spectroscopy (IR) is also a powerful method to examine carboxylate coordination modes [47][48]. As can be seen (Table 1), the present complexes reveal two

• (“gauche” conformation) most likely due to steric constraints exerted by the surrounding NMe groups. We have observed similar effects in an azido-bridged complex, where the surrounding alkyl groups dictate the coordination mode of the azido ligand [49]. Figure 3 provides a ball and stick and a van der

Synthesis of [Fe(L_eq)(L_ax)]_n coordination polymer nanoparticles using blockcopolymer micelles

• Christoph Göbel,
• Ottokar Klimm,
• Florian Puchtler,
• Sabine Rosenfeldt,
• Stephan Förster and
• Birgit Weber

Beilstein J. Nanotechnol. 2017, 8, 1318–1327, doi:10.3762/bjnano.8.133

• temperature. Applications demand compounds with defined properties concerning the size and switchability that are maintained when the compound is integrated into composite materials. Here, we report the synthesis of [Fe(Leq)(Lax)]n coordination polymer (CP) nanoparticles using self-assembled polystyrene-block

• (bpea)]n@BCP while pronounced differences are observed in the case of [FeLeq(bpey)]n@BCP nanoparticles. Keywords: block copolymer; composite; nanoparticles; self-assembly; spin crossover; Introduction Nanomaterials and especially nanocomposites of coordination polymers (CPs) and (porous) coordination

• (mostly magnetite) [12]. For coordination polymers (CP) or networks a limited amount of methods are applicable because of the very demanding reaction conditions and/or incompatible reactants. Recently we demonstrated that the use of block copolymers (BCPs) is a highly promising and easy approach for the

Atomic structure of Mg-based metallic glass investigated with neutron diffraction, reverse Monte Carlo modeling and electron microscopy

• Rafał Babilas,
• Dariusz Łukowiec and
• Laszlo Temleitner

Beilstein J. Nanotechnol. 2017, 8, 1174–1182, doi:10.3762/bjnano.8.119

• pair correlation functions and coordination numbers, which illustrated some types of cluster packing. The N = 9 clusters correspond to the tri-capped trigonal prisms, which are one of Bernal’s canonical clusters, and atomic clusters with N = 6 and N = 12 are suitable for octahedral and icosahedral

• separation in the studied glass after heat treatment. The HAADF mode allows for the observation of randomly distributed, dark contrast regions of about 4–6 nm. The interplanar spacing identified for the orthorhombic Mg2Cu crystalline phase is similar to the value of the first coordination shell radius from

• coordination shell. The R can be calculated by using following formula λ/2sinθ*, where 2θ* is the scatter angle at the halo maximum and λ is the wavelength [25]. The value of R = 0.242 nm can be compared with the atomic radii of the Mg, Cu, Y and Ni elements, which is 0.160, 0.128, 0.180 and 0.124 nm

Preparation of thick silica coatings on carbon fibers with fine-structured silica nanotubes induced by a self-assembly process

• Benjamin Baumgärtner,
• Hendrik Möller,
• Thomas Neumann and
• Dirk Volkmer

Beilstein J. Nanotechnol. 2017, 8, 1145–1155, doi:10.3762/bjnano.8.116

• ], or by introducing acidic and basic additives that can interact with LPEI [22] and other proton donors [23]. Further modification of the silica morphology can be achieved by adding metal ions that form complexes with the secondary amine groups of LPEI [24][25][26]. The coordination interactions

Structural properties and thermal stability of cobalt- and chromium-doped α-MnO₂ nanorods

• Romana Cerc Korošec,
• Polona Umek,
• Alexandre Gloter,
• Jana Padežnik Gomilšek and
• Peter Bukovec

Beilstein J. Nanotechnol. 2017, 8, 1032–1042, doi:10.3762/bjnano.8.104

• is 3+ as in Cr2O3 [29]. The spectra of the samples at the same edge are very similar, showing no major changes of metal coordination during the heating. There is a slight shift of the Mn and Co edges in the Co-90 sample toward lower energies, i.e., to a smaller oxidation number. In the spectrum of Cr

• simultaneous fits of all spectra of the same ion. In the three final models, the number of oxygen neighbors was set to 6 in all cases. For all spectra in the model, we used the same values for the energy shift E0, the amplitude parameter S02, path lengths ri and coordination numbers Ni of manganese neighbors

• metal oxidation states. As already mentioned, doping of the α-MnO2 structure can take place either in the Mn–O framework where dopant ions substitute manganese ions, or in the tunnels where they substitute potassium cations. This depends on the ionic radii of the dopant ions and their coordination [14

Study of the correlation between sensing performance and surface morphology of inkjet-printed aqueous graphene-based chemiresistors for NO₂ detection

• F. Villani,
• C. Schiattarella,
• T. Polichetti,
• R. Di Capua,
• F. Loffredo,
• B. Alfano,
• M. L. Miglietta,
• E. Massera,
• L. Verdoliva and
• G. Di Francia

Beilstein J. Nanotechnol. 2017, 8, 1023–1031, doi:10.3762/bjnano.8.103

• the case of graphene the active sites are represented by sp2 carbon atoms (low interaction energy) and defects such as vacancies, dangling bonds, coordination defects and functionalizations (high interaction energy). In the specific case of our LPE graphene, defects are mostly ascribed to edge defects