Impact of Li, Na and Zn metal cation concentration in EMIM-TFSI ionic liquids on ion clustering, structure and dynamics.

We use molecular dynamics calculations to investigate the behavior of metal cations (Li, Na and Zn) within ionic liquids (ILs), specifically EMIM-TFSI, and their impact on key properties, particularly focusing on ion-ion correlations and their influence on diffusion and conductivity. The study explores the competition between metal cations and EMIM ions for binding to TFSI and analyzes ion pair dynamics, revealing that metal cation-TFSI pairs exhibit significantly longer lifetimes compared to TFSI-EMIM pairs. This competitive interaction and the increased stability of metal cation-TFSI pairs at higher concentrations leads to reduced ion exchange, resulting in decreased diffusion and conductivity.

Chain Formation during Hydrogen Loss and Reconstruction in Carbon Nanobelts.

Using laser-induced vaporisation to evaporate and ionise a source of curved polyaromatic hydrocarbons (carbon nanobelts), we show collision impacts between species cause mass loss and the resultant ions are catalogued via mass-spectrometry. These data are interpreted via a series of "in-silico"-simulated systematic hydrogen-loss studies using density functional theory modelling, sequentially removing hydrogen atoms using thermodynamic stability as a selection for subsequent dehydrogenation. Initial hydrogen loss results in the formation of carbyne chains and pentagon-chains while the nanobelt rings are maintained, giving rise to new circular strained dehydrobenzoannulene species.

TD-DFT and CC2 insights into the dual-emissive behaviour of 2-(2'-hydroxyphenyl)oxazoles core and their derivatives.

Two efficient excited state intramolecular proton transfer (ESIPT) dyes based on the hydroxyphenyl-oxazole core and containing one or two triphenylamine donor groups are explored with theoretical tools. These compounds are known to show clear experimental dual emission behaviour, leading to nearly pure white-light emission for one derivative. To probe the excited state properties, we use both Time Dependent Density Functional Theory (TD-DFT) and post Hartree-Fock methods [ADC(2) and CC2] coupled to different solvent models to describe polarisation effects.

Dual fluorescence in strap ESIPT systems: a theoretical study.

Alkylamine-strapped chromophores based on a dithienylpyrrole core, and in which the Excited State Intramolecular Proton Transfer (ESIPT) process yields a zwitterionic structure rather than a keto tautomer have been reported recently (Suzuki et al., Angew. Chem.

Determining addition pathways and stable isomers for CF functionalization of endohedral Gd@C.

Using density functional theory approaches, we follow the sequential addition of CF functional groups to the surface of the metallic endofullerene species Gd@C. The presence of gadolinium in the interior of the cage strongly influences the addition sequence. The calculations are able to successfully identify end points in the addition sequence at Gd@C(CF) , = 3 and two isomers at = 5, in predictive agreement with experiment.

Isolation and structure determination of missing fullerenes Gd@C(CF) through trifluoromethylation.

Our trifluoromethyl functionalization method enables the dissolution and isolation of missing metallofullerenes of Gd@C(CF) . After multi-stage high-performance liquid chromatography purification, Gd@C(CF) and two regioisomers of Gd@C(CF) are isolated. X-ray crystallographic analysis reveals that all of the isolated metallofullerenes react with CF groups on pentagons of the -symmetry C cages.

Accurate control of the covalent functionalization of single-walled carbon nanotubes for the electro-enzymatically controlled oxidation of biomolecules.

Single-walled carbon nanotubes (SWCNTs) were functionalized by ferrocene through ethyleneglycol chains of different lengths (FcETGn) and the functionalized SWCNTs (f-SWCNTs) were characterized by different complementary analytical techniques. In particular, high-resolution scanning electron transmission microscopy (HRSTEM) and electron energy loss spectroscopy (EELS) analyses support that the outer tubes of the carbon-nanotube bundles were covalently grafted with FcETGn groups. This result confirms that the electrocatalytic effect observed during the oxidation of the reduced form of nicotinamide adenine dinucleotide (NADH) co-factor by the f-SWCNTs is due to the presence of grafted ferrocene derivatives playing the role of a mediator.

Crystalline functionalized endohedral C metallofullerides.

Endohedral metallofullerenes have been extensively studied since the first experimental observation of La@C in a laser-vaporized supersonic beam in 1985. However, most of these studies have focused on metallofullerenes larger than C such as (metal)@C, and there are no reported purified C-based monomeric metallofullerenes, except for [Li@C](SbCl) salt. Pure (metal)@C compounds have not been obtained because of their extremely high chemical reactivity.

Electronic Communication between two [10]cycloparaphenylenes and Bis(azafullerene) (C N) Induced by Cooperative Complexation.

The complex of [10]cycloparaphenylene ([10]CPP) with bis(azafullerene) (C N) is investigated experimentally and computationally. Two [10]CPP rings are bound to the dimeric azafullerene giving [10]CPP⊃(C N) ⊂[10]CPP. Photophysical and redox properties support an electronic interaction between the components especially when the second [10]CPP is bound.

Spectromicroscopy of C and azafullerene CN: Identifying surface adsorbed water.

C fullerene crystals may serve as important catalysts for interstellar organic chemistry. To explore this possibility, the electronic structures of free-standing powders of C and (CN) azafullerenes are characterized using X-ray microscopy with near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy, closely coupled with density functional theory (DFT) calculations. This is supported with X-ray photoelectron spectroscopy (XPS) measurements and associated core-level shift DFT calculations.

Ab initio infrared vibrational modes for neutral and charged small fullerenes (C20, C24, C26, C28, C30 and C60).

We calculate the infrared (IR) absorption spectra using DFT B3LYP(6-311G) for a range of small closed-cage fullerenes, Cn, n=20, 24, 26, 28, 30 and 60, in both neutral and multiple positive and negative charge states. The results are of use, notably, for direct comparison with observed IR absorption in the interstellar medium. Frequencies fall typically into two ranges, with C-C stretch modes around 1100-1500 cm(-1) (6.

A Complete Overhaul of the Electron Energy-Loss Spectroscopy and X-Ray Absorption Spectroscopy Database: eelsdb.eu.

The electron energy-loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) database has been completely rewritten, with an improved design, user interface, and a number of new tools. The database is accessible at https://eelsdb.eu/ and can now be used without registration.

Atomic configuration of nitrogen-doped single-walled carbon nanotubes.

Having access to the chemical environment at the atomic level of a dopant in a nanostructure is crucial for the understanding of its properties. We have performed atomically resolved electron energy-loss spectroscopy to detect individual nitrogen dopants in single-walled carbon nanotubes and compared with first-principles calculations. We demonstrate that nitrogen doping occurs as single atoms in different bonding configurations: graphitic-like and pyrrolic-like substitutional nitrogen neighboring local lattice distortion such as Stone-Thrower-Wales defects.

Synthesis of substituted [8]cycloparaphenylenes by [2 + 2 + 2] cycloaddition.

A new modular approach to the smallest substituted cycloparaphenylenes (CPPs) is presented. This versatile method permits access to substituted CPPs, choosing the substituent at a late stage of the synthesis. Variously substituted [8]CPPs have been synthesized, and their properties analyzed.

Towards atomic resolution in sodium titanate nanotubes using near-edge X-ray-absorption fine-structure spectromicroscopy combined with multichannel multiple-scattering calculations.

Recent advances in near-edge X-ray-absorption fine-structure spectroscopy coupled with transmission X-ray microscopy (NEXAFS-TXM) allow large-area mapping investigations of individual nano-objects with spectral resolution up to E/ΔE = 10(4) and spatial resolution approaching 10 nm. While the state-of-the-art spatial resolution of X-ray microscopy is limited by nanostructuring process constrains of the objective zone plate, we show here that it is possible to overcome this through close coupling with high-level theoretical modelling. Taking the example of isolated bundles of hydrothermally prepared sodium titanate nanotubes ((Na,H)TiNTs) we are able to unravel the complex nanoscale structure from the NEXAFS-TXM data using multichannel multiple-scattering calculations, to the extent of being able to associate specific spectral features in the O K-edge and Ti L-edge with oxygen atoms in distinct sites within the lattice.

X-ray absorption spectroscopy by full-field X-ray microscopy of a thin graphite flake: Imaging and electronic structure via the carbon K-edge.

We demonstrate that near-edge X-ray-absorption fine-structure spectra combined with full-field transmission X-ray microscopy can be used to study the electronic structure of graphite flakes consisting of a few graphene layers. The flake was produced by exfoliation using sodium cholate and then isolated by means of density-gradient ultracentrifugation. An image sequence around the carbon K-edge, analyzed by using reference spectra for the in-plane and out-of-plane regions of the sample, is used to map and spectrally characterize the flat and folded regions of the flake.

Low-energy termination of graphene edges via the formation of narrow nanotubes.

We demonstrate that free graphene sheet edges can curl back on themselves, reconstructing as nanotubes. This results in lower formation energies than any other nonfunctionalized edge structure reported to date in the literature. We determine the critical tube size and formation barrier and compare with density functional simulations of other edge terminations including a new reconstructed Klein edge.

Stability, thermal homolysis and intermediate phases of solid hydroazafullerene C59HN.

Density functional (DFT) calculations, high-temperature electron paramagnetic resonance (EPR) and transmission electron microscopy (TEM) results suggest that thermal homolysis of C59HN involves a remarkably stable intermediate C59N-C59HN* structure characterised by charge redistribution from a C59N* radical to a bonded C59HN.

Pattern formation on carbon nanotube surfaces.

Calculations of fluorine binding and migration on carbon nanotube surfaces show that fluorine forms varying surface superlattices at increasing temperatures. The ordering transition is controlled by the surface migration barrier for fluorine atoms to pass through next neighbor sites on the nanotube, explaining the transition from semi-ionic low coverage to covalent high coverage fluorination observed experimentally for gas phase fluorination between 200 and 250 degrees C. The effect of solvents on fluorine binding and surface diffusion is explored.