Synthesis and Photophysical Properties of a Sc3N@C80‐Corrole Electron Donor–Acceptor Conjugate

Embedding endohdedral metallofullerenes (EMFs) into electron donor–acceptor systems is still a challenging task owing to their limited quantities and their still largely unexplored chemical properties. In this study, we have performed a 1,3‐dipolar cycloaddition reaction of a corrole‐based precursor with Sc₃N@C₈₀ to regioselectively form a [5,6]‐adduct ( 1 ). The successful attachment of the corrole moiety was confirmed by mass spectrometry. In the electronic ground state, absorption spectra suggest sizeable electronic communications between the electron acceptor and the electron donor. Moreover, the addition pattern occurring at a [5,6]‐bond junction is firmly proven by NMR spectroscopy and electrochemical investigations performed with 1 . In the electronically excited state, which is probed in photophysical assays with 1 , a fast electron‐transfer yields the radical ion pair state consisting of the one‐electron‐reduced Sc₃N@C₈₀ and of the one‐electron‐oxidized corrole upon its exclusive photoexcitation. As such, our results shed new light on the practical work utilizing EMFs as building blocks in photovoltaics.     

Discovery of a new long-lived isomeric state in 125Ce

A new long-lived isomeric state in the near proton dripline nucleus ¹²⁵Ce has been identified with Schottky mass spectrometry at GSI. The excitation energy E ^* = 103(12)keV and the decay time of 193(1)s have been obtained from a single stored fully ionized ^125m Ce⁵⁸⁺ ion. The data implies an E3 transition and a 1/2⁺ assignment for the spin of the isomer.     

Über grünes Bis-(2-Iminoisopropyl-thiophenolato)-nickel(II) und weitere, ähnliche NiII-Komplexe

Green Bis-(2-iminoisopropyl-thiophenolato)nickel(II) and other Similar Ni^II Complexes The compounds [Ni^II(iitp)₂] 1 (iitp = 2-iminoisopropyl-thiophenolate), [Ni(imptp)₂] · 2 CH₃OH 2 , a dinuclear compound with an Ni? Ni distance of 276 pm, and [PPh₄] · [Ni^II(imptp)(SCN)] 3 (imptp = 2-(2-iminopentane-4-on)-thiophenolate) have been prepared by the reaction of nickel(II)-acetate-tetrahydrate with 2-iminoisopropyl-thiophenole and 2-(2-iminopentane-4-on)-thiophenole in methanol, respectively. They have been characterized by single-crystal X-ray structure analysis and other physical methods. The redox behaviour of 1–3 has been studied in detail (chemically as well as by cyclovoltammetry and ESR spectroscopy). Particularly interesting are the electronic properties of 1 and its reduction with NaBH₄ and the following reaction of the product with O₂. The complexes are model compounds for some Ni-containing enzymes. For details of the crystal structure determination see “Inhaltsübersicht”.     

Copper(II) Complexes of ω‐Hydroxy‐Functionalized N‐Salicylidenehydrazides show pH‐Controlled Switching between Dicationic Dimers and Neutral One‐Dimensional Coordination Polymers

New copper(II) complexes of the hydrazone ligands H₂salhyhb, H₂salhyhp, and H₂salhyhh, derived from salicylaldehyde and ω‐hydroxy carbonic acid hydrazides, have been synthesized and physically characterized. Two fundamental structures were found in solid state depending on the pH‐value of the reaction solution. Acidic conditions lead to the formation of the di‐μ‐phenoxo‐bridged dicationic complex dimers [{Cu(Hsalhyhb)}₂]²⁺ ( 1a ), [{Cu(Hsalhyhp)}₂]²⁺ ( 2a ), and [{Cu(Hsalhyhh)}₂]²⁺ ( 3a ), isolated as perchlorate salts. The dimeric complexes show strong antiferromagnetic coupling with J = ?399 ( 1a ), ?410 ( 2a ), and ?311 cm^?1 ( 3a ). Higher pH‐values resulted in the aggregation of neutral copper ligand fragments to the one‐dimensional coordination polymers [{Cu(salhyhb)}_n] ( 1b ), [{Cu(salhyhp)}_n] ( 2b ), and [{Cu(salhyhh)}_n] ( 3b ). 3b has been examined by means of X‐ray crystallography and represents the first example of a structurally characterized neutral copper(II) N‐salicylidenehydrazide complex without additional ligands. The magnetic interactions in the polymers are also antiferromagnetic with J = ?125 ( 1b ), ?136 ( 2b ), and ?148 cm^?1 ( 3b ), but strongly reduced compared to the corresponding dimeric complexes. The two basic structure types can be reversibly interconverted simply by pH‐control.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

2,2-Difluor-1,2,3-trimethyl-1,3-diaza-2λ5-phospholidin

2,2-Difluoro-1,2,3-trimethyl-1,3-diaza-2λ⁵-phospholidine The title compound 1 is obtained in about 50% yield by oxidative fluorination of 1,2,3-trimethyl-1,3-diaza-2λ³-phospholidine, 6 , with IF₅. 1 is characterized by its nmr, mass, and ir spectra.     

Chemical mass shifts in resonance ejection experiments in the quadrupole ion trap

Chemical mass shifts were measured in a Paul ion trap operated in the mass-selective instability scan with resonance ejection using a custom-built instrument. These shifts, which can be as much as 2%, decrease with increasing endcap electrode separation owing to changes in the higher order contributions to the electric field. They also decrease with decreasing helium buffer gas pressure. Both of these effects are analogous to those found with boundary ejection. This suggests that the previously proposed chemical mass shift mechanism based on compound-dependent collisional modification of the ejection delay produced by field faults near the endcap electrode apertures holds true also for resonance ejection. The influence of the resonance frequency on chemical mass shifts was also investigated and it is shown that at certain working points (values of the Mathieu parameter q(z) and a(z)) non-linear resonances greatly reduce the ejection delay for all ions, regardless of their chemical structures, and thus reduce the magnitude of the chemical mass shift. Energetic collisions leading to dissociation can take place at an earlier stage during the ejection process in the mass analysis scan when using resonance ejection compared with boundary ejection. This leads to even larger chemical mass shifts of fragile ions in resonance ejection. Increasing the resonance voltage amplitude can enhance this effect. The chemical mass shifts of fragile ions increase with increase in the resonance voltage amplitude, whereas negligible changes occur for structurally stable ions.     

Narrow band quantitative and multivariate electroencephalogram analysis of peri-adolescent period

ABSTRACT: BACKGROUND: The peri-adolescent period is a crucial developmental moment of transition from childhood to emergent adulthood. The present report analyses the differences in Power Spectrum (PS) of the Electroencephalogram (EEG) between late childhood (24 children between 8 and 13 years old) and young adulthood (24 young adults between 18 and 23 years old). RESULTS: The narrow band analysis of the Electroencephalogram was computed in the frequency range of 0--20 Hz. The analysis of mean and variance suggested that six frequency ranges presented a different rate of maturation at these ages, namely: low delta, delta-theta, low alpha, high alpha, low beta and high beta. For most of these bands the maturation seems to occur later in anterior sites than posterior sites. Correlational analysis showed a lower pattern of correlation between different frequencies in children than in young adults, suggesting a certain asynchrony in the maturation of different rhythms. The topographical analysis revealed similar topographies of the different rhythms in children and young adults. Principal Component Analysis (PCA) demonstrated the same internal structure for the Electroencephalogram of both age groups. Principal Component Analysis allowed to separate four subcomponents in the alpha range. All these subcomponents peaked at a lower frequency in children than in young adults. CONCLUSIONS: The present approaches complement and solve some of the incertitudes when the classical brain broad rhythm analysis is applied. Children have a higher absolute power than young adults for frequency ranges between 0-20 Hz, the correlation of Power Spectrum (PS) with age and the variance age comparison showed that there are six ranges of frequencies that can distinguish the level of EEG maturation in children and adults. The establishment of maturational order of different frequencies and its possible maturational interdependence would require a complete series including all the different ages.