Reverse phenomena of magnetic field effects and time-resolved EPR spectra in the photogenerated biradical from intramolecular electron-transfer in a phenothiazine–C60 linked compound with a semi-rigid spacer

Photoinduced electron-transfer reactions and magnetic field effects (MFEs) on the decay rates of the photogenerated biradical in a phenothiazine (Ph)–C₆₀ linked compound with a biphenyl group (Ph(BP)C₆₀) were examined in benzonitrile and benzene. Fluorescence and transient absorption spectra indicate that the intramolecular electron-transfer for Ph(BP)C₆₀ from the Ph to the singlet or triplet excited state of C₆₀ was suppressed by the biphenyl group. The decay rates of the photogenerated biradical decreased in the 0–0.2 T magnetic field range and increased in the 0.2–1 T magnetic field range. The reverse phenomena of the MFEs in Ph(BP)C₆₀ were strongly enhanced with increasing temperature and similar to those in Ph(n)C₆₀ (n = 6?12). The MFEs in Ph(BP)C₆₀ can be governed by spin-lattice relaxation and/or spin-spin relaxation mechanisms as observed in Ph(n)C₆₀ (n = 6?12). Time-resolved EPR spectra of Ph(BP)C₆₀ showed absorption, emission, absorption and emission patterns, and are quite different from those in Ph(n)C₆₀ (n = 4?12). The result indicates that the magnitude and distribution of the exchange interaction |2J| in Ph(BP)C₆₀ are smaller than those in Ph(n)C₆₀ (n = 4?12) and charge recombination occurs in the inverted region because the sign of the J is positive.     

Photoinduced intramolecular electron transfer reactions in fullerene—phenothiazine linked compounds: effects of magnetic field and spacer chain length

Spectroscopic and electrochemical properties of two fullerene(C₆₀)-phenothiazine(PH) linked compounds with different spacer chain length have been compared in benzonitrile (polar solvent) and in benzene (non-polar solvent). Transient absorption and fluorescence spectra indicated that photoinduced intramolecular electron transfer occurred in benzonitrile, but not in benzene. The results are due to solvent effect on energy levels of the photogenerated biradical. The driving forces for the electron transfer were determined by measuring the redox potentials of the C₆₀ and PH moieties. Thermodynamic parameters for the electron transfer processes were evaluated and compared. In benzonitrile, the lifetime of the photo-generated biradical was very long, in spite of being around the top region in Marcus theory. The decay rate of the biradicals was retarded in the presence of magnetic fields. The decay rate constant decreased quickly with increasing the magnetic field and became constant above about 0.2 T. The magnetic field effects verified that the triplet biradical was generated by the intramolecular electron transfer from PH to the triplet excited state of C₆₀. The long lifetime is most probably ascribed to the spin multiplicities of the biradical.     

Structures and electronic states of photoexcited states in a system of two nitroxide radicals linked to fullerene studied by two-dimensional pulsed nutation and time-resolved electron paramagnetic resonance spectroscopy

Magnetic properties of fulleropyrrolidine adducts with two stable nitroxide radicals (2,2,6,6-tetramethylpiperidine-1-oxyl, TEMPO) were studied in toluene solution by continuous-wave time-resolved (TR) and pulsed electron paramagnetic resonance (EPR) spectroscopy in the ground and photoexcited states. Four isomers of the bisadduct,trans-1,trans-2,trans-3, and equatorial forms, having the second pyrrolidine ring at different [6-6] bonds were synthesized. In the ground states, the exchange interaction between two TEMPOs is so small that the spin state of the bisadduct is a doublet in nature. By means of spectral simulations of the EPR spectra in frozen solution at 70 K, the upper limit of the exchange interaction was estimated to be 5 MHz for thetrans-1 andtrans-2 and 10 MHz for thetrans-3 and equatorial isomers. The simulation was also made to determine relative positions of the two TEMPO groups with respect to the pyrrolidine ring. Photoexcited states of the bisadducts with excitation of the 532 nm laser pulse were studied in frozen toluene solution at 5–100 K by using two-dimensional (2-D) pulsed nutation EPR and TREPR. The spin multiplicity of the excited state was determined by the nutation frequency. All of the four bisadducts showed strong exchange couplings between two TEMPOs and fullerene triplet³C ₆₀ ^* , resulting in the generation of the excited quintet and triplet states. The excited triplet states have been observed and assigned for the first time in strongly coupled triplet-radical systems. The zero-field splittings of the quintet state determined from the 2-D nutation EPR spectra were analyzed as the sum of the spinspin interactions among the three paramagnetic centers, two TEMPOs and³C ₆₀ ^* . On the basis of these analyses, the spin distribution on the³C ₆₀ ^* part and the geometry of two TEMPOs are discussed.     

Mössbauer study of the hyperfine and magnetic properties of organo-di-iron electron reservoirs containing a polyaromatic bridging ligand

Organo di-iron electron reservoirs Fe(CP^*)₂(Ar) ⁿ⁺ withn=2, 1, 0, where Cp^* is C₅(CH₃)₅ and where Ar are the following bridges: biphenyl, dihydrophenanthrene, triphenylene, have been studied by Mössbauer spectroscopy in the solid state. Complexes withn=2, with 36e^? in the coordination spheres of the metals, exhibit the usual diamagnetic behaviour of 18e^?, Fe^II mono-iron systems. Complexes withn=1, 37e^?, are delocalized mixed valence (Fe^IIFe^I) with a spin 1/2; the magnetic hyperfine interaction, measured under an external field, shows equal delocalization of the 37^th e^? on the two iron centers and the two bridging carbon atoms of the biphenylene. Complexes withn=0, formally with 38e^?, have a practically temperature-independent quadrupole splitting, and isomer shift values which constrast with the expected behaviour of independent Fe^I, 19e^? centers. This indicates that the 37^th and 38^th electrons are mostly located on the polyaromatic bridge. Spectra obtained in an external field show a negligible magnetic hyperfine interaction and support this conclusion. In the case of biphenyl and dihydrophenanthrene bridges, this electron localization can be related to a strong intramolecular chemical coupling, evidenced by other spectroscopic and X-ray data [1].     

Stoichiometric synthesis of fullerene compounds with lithium and sodium and analysis of their IR and EPR spectra

A modified method is proposed for preparing fullerene compounds with alkali metals in a solution. The compounds synthesized have the general formula Me _n C₆₀(THF)_x, where Me = Li or Na; n=1–4, 6, 8, or 12; and THF = tetrahydrofuran. The use of preliminarily synthesized additives MeC₁₀H₈ makes it possible to prepare fullerene compounds with an exact stoichiometric ratio between C ₆₀ ^n? and Me ⁺. The IR and EPR spectra of the compounds prepared are analyzed and compared with the spectra of their analogs available in the literature. The intramolecular modes T _u (1)-T _u (4) for the C ₆₀ ^n? anion are assigned. The splitting of the T _u (1) mode into a doublet at room temperature for Me _n C₆₀(THF)_x (n=1, 2, 4) compounds indicates that the fullerene anion has a distorted structure. An increase in the intensity of the T _u (2) mode, a noticeable shift of the T _u (4) mode toward the long-wavelength range, and an anomalous increase in the intensity of the latter mode for the Li₃C₆₀(THF)_x complex suggest that, in the fullerene anion, the coupling of vibrational modes occurs through the charge-phonon mechanism. The measured EPR spectra of lithium-and sodium-containing fullerene compounds are characteristic of C ₆₀ ^? anions. The g factors for these compounds are almost identical and do not depend on temperature. The g factor for the C ₆₀ ^n? anion depends on the nature of the metal and differs from the g factor for the C ₆₀ ^? anion.     

Optical and time-resolved electron paramagnetic resonance studies of the excited states of para-methylcinnamic acid and para-methylcinnamate anion

Time-resolved electron paramagnetic resonance (EPR), fluorescence, and phosphorescence spectra have been observed for the excited states oftrans-p-methylcinnamic acid (p-MeCA) andtrans-p-methylcinnamate anion (p-MeCA^?) in rigid organic glasses at 77 K. With a stretched-polymer-film technique, we assigned the resonance fields in the time-resolved EPR spectra of the lowest excited triplet (T₁) states ofp-MeCA andp-MeCA^?. From the analysis of these spectra we concluded that the deviation from planar structure in the T₁ state is small inp-MeCA andp-MeCA^? and the direction of C=O iss-cis to the ethylenic C=C bond inp-MeCA. The deprotonation appears to have little effect on the zero-field splitting (ZFS) parameters. The ZFS parameters were calculated theoretically using semiempirical molecular orbitals. The sublevel preferentially populated by intersystem crossing (ISC) is T _y in bothp-MeCA andp-MeCA^?. However, following the deprotonation ofp-MeCA, (P _y?P _z)/(P _x?P _z) changes from 5.7 inp-MeCA to 2.1 inp-MeCA^? (P _i are relative populating rates; thex andy axes are close to the long and short in-plane molecular axes, respectively, andz-axis is perpendicular to the molecular plane). The fluorescence lifetimes indicate that the deprotonation has little effect on the sum of the three ISC rate constants for the three T₁ sublevels. A decrease in acidity ofp-MeCA upon excitation has been observed.     

Isotopieverschiebungskonstanten von Th,U, Pu und Am

The isotope shifts of unperturbed electron configurations have been determined from isotope shift measurements in the spectra of Th, U, Pu, and Am. The screening of the 7s electron charge density at the nucleus by 6d, 7s, and 7p electrons is discussed. It turns out that the same screening factors as for the 6s electron in lighter elements can be used. The screening of the 7s electron charge density at the nucleus by one 5f electron amounts to about 25%: [δT(f ⁿ s)?δT(f ⁿ )]/[δT(f ⁿ }s)?δ(f ^n} )]=0.7₅. The charge density at the nucleus due to the filleds (andp _1/2) shells is considerabely screened by anf electron. The isotope shiftδT(f^n}-1 d ^m +2)?δT(f ⁿ d ^m ) produced by this effect is of the same order of magnitude as the isotope shiftδT(f ⁿ d ^m s)-δT(f ⁿ d ^m ) due to ans electron. The experimental isotope shift constants are found to be:Β C _exp(Th²³⁰–Th²³²)=880±120;Β C _exp(U²³³–U²³⁵)=1000±180;Β C _exp(U²³⁴–U²³⁶)=1070±200;Β C _exp(U²³⁶–U²³⁸)=1080±180;Β C _exp(Pu²³⁸–Pu²⁴⁰)=1200±120;Β C _exp(Pu²³⁹–Pu²⁴¹)=1060±100;Β C _exp(Pu²⁴⁰–Pu242)=900 ±90;Β C _exp(Am²⁴¹–Am²⁴³)=890±50 [10^?3cm^?1]. The ratiosΒ C _exp/C _th are discussed.     

Thermal neutron induced α-particle reaction on64, 65, 67Zn and77Se

The (_n th,α) reaction spectroscopy was done on^{64, 65, 67}zn and⁷⁷Se at the 87 m curved thermal neutron guide of the Grenoble high flux reactor. In each of the⁶⁴Zn(n, α)⁶¹ Ni and⁶⁷ Ni(n, α) ⁶⁴Ni reactions, one line showed up corresponding to anα-particle transition to the first excited state in⁶¹Ni and⁶⁴Ni withσ _α1=11±3 μb and 159±20 μb respectively. In the case of the radioactive⁶⁵Zn(T _1/2=244d) nucleus, two lines showed up corresponding to the ground state and the first excited state transitions in⁶²Ni with large values ofσ _α0=1.0±0.1b andσ _α1=1.0±0.1b. For the⁷⁷Se(n, α)⁷⁴Ge reaction, the ground state and first excited transitions were present withσ _α0=940±20 μb andσ _α1 = 30±5 μb respectively. The spin-parity (J ^π) of the neutron resonance contributing at thermal energy are discussed.     

A study of fusion reactions between206, 207Pb nuclei and40Ar ions near the coulomb barrier

Excitation functions for the reactions²⁰⁶Pb(⁴⁰Ar, 2n)²⁴⁴Fm and²⁰⁷Pb(⁴⁰Ar, 3n)²⁴⁴Fm have been measured and analysed in terms of a statistical model. The optical potential parameters have been found to be as follows:V ₀=? 70 MeV,r ₀=1.26×10^?13 cm andd =0.36×10^?13 cm. Some data on the properties of the excited compound nucleus of fermium have been obtained.     

On the energy dependence of the yield of doubly charged negative ions during the capture of free electrons by C60(CF3)12 trifluoromethylfullerene molecules

Peaks of C₆₀(CF₃) _n ^2? doubly charged negative ions (n = 6–12) have been observed in the mass spectra of the resonance electron capture by trifluoromethylfullerene C₆₀(CF₃)₁₂ molecules. It has been established that these ions are formed owing to the attachment of two free isoenergetic electrons. The autodetachment of an extra electron has been detected for the doubly charged molecular ions (n = 12). It has been established from the observation of the delayed fragmentation of the most abundant ions with n = 8 and 10 that the doubly charged negative ions, like their singly charged analogs, are metastable with respect to the separation of the CF₃ fragment(s). The yield of doubly charged negative ions has been obtained as a function of the electron energy. By comparing them with the analogous dependences for the singly charged ions, the specific features have been revealed which were associated with the presence of the repulsive Coulomb barrier and the regular effect of the doubled energy of two additional electrons on the energy dependence of the dissociative decay of the doubly charged negative ions. The absolute cross section for the formation of the C₆₀(CF₃) ₁₀ ^2? ions has been measured. At the energy of their yield maximum near the 5 eV, it is ～1 × 10^?19 cm².     

Effective, fast, and low temperature encapsulation of fullerene derivatives in single wall carbon nanotubes

High filling of single wall nanotubes (SWCNTs) with the typical exohedrally functionalized fullerene derivative of C₆₀N-methyl-3,4-fulleropyrrolidine C₆₀-C₃NH₇ is reported at the temperature of refluxing hexane. The new peapod material is characterized by STM (scanning tunneling microscopy), TEM (transmission electron microscopy) and Raman spectroscopy. Atomically resolved STM scans on SWCNT show no excessive defects or sidewall functionalization as a result of this treatment. The radial breathing mode (RBM) mode of SWCNT at 165 cm⁻¹ becomes weaker and shifted to 169 cm⁻¹ indicating filled nanotubes. TEM studies show bundles of SWCNT are highly filled with derivative C₆₀-C₃NH₇ and form the (C₆₀-C₃NH₇)_n peapods. Individual pyrrolidine-type functional groups attached to the fullerene cages are unambiguously visualized by a lower-dose observation.     

Excitation functions of nuclear reactions producing11C

Excitation functions of the reactions⁹Be(³He,n),¹⁰B(d,n),¹¹B(p,n),⁹Be(α,2n),¹¹B(d,2n) and¹²C(n,2n), all leading to the residual nucleus¹¹C, were measured with activation techniques. Projectile energies have been chosen to populate the composite systems¹²C^* and¹³C^* in energy ranges overlapping for 31MeV≦E ^*(¹²C)≦38MeV and 26 MeV≦E ^*(¹³C)≦33Mev, respectively. The attainable thick target yields are highest forp+¹¹B. Statistical model calculations fail to quantitatively reproduce the experimental data although preequilibrium decay modes have been taken into account.     

Spectroscopy of excited states in212Po,210Pb,and213At employing18O induced few-nucleon transfer reactions

γ-ray spectroscopic techniques have been applied to measure properties of excited states (E ^*<2MeV) in²¹⁰Pb,²¹²Po, and²¹³At after populating these neutron rich (N=128) nuclei via¹⁸O induced few-nucleon transfer reactions on²⁰⁸Pb and²⁰⁹Bi targets. In²¹²Po an isomeric state is located atE ^*=1,477 keV with a halflife oft _1/2=14.7±0.3 ns. This state is interpreted to be the 8⁺ yrast level which decays to the ground state via the measured $$8^ + \left( {121.1 keV} \right)6^ + \left( {223.3 keV} \right)4^ + \left( {405.1 keV} \right)2^ + \left( {727.8 keV} \right)0^ + $$ γ-cascade.α-decay (E _α≈10.2 MeV) of the isomer is also observed. In²¹⁰Pb the time spectra for members of the 4⁺ (297.8keV) 2⁺ (799.4keV)0⁺ γ-cascade show a delayed component with a halflife oft _1/2=152±13 ns which is attributed to the known 8⁺ yrast state atE ^*=1.27 MeV. For²¹³At first results on theγ-decay of excited states are presented.     

Polar smectic subphases: Phase diagrams, structures and X-ray scattering

We analyze a discrete phenomenological model accounting for phase transitions and structures of polar Smectic-C* liquid-crystalline phases. The model predicts a sequence of phases observed in experiment: antiferroelectric SmC _A ^* –ferrielectric SmC _FI1 ^* –antiferroelectric SmC _FI2 ^* (three-and four-layer periodic, respectively)–incommensurate SmC _α ^* –SmA. We find that, in the three-layer SmC _FI1 ^* structure, both the phase and the module of the order parameter (tilt angle) differ in smectic layers. This modulation of the tilt angle (and therefore of the layer spacing d) must lead to X-ray diffraction at the wave vectors Q _s =2πs/d(s=n±1/3) even for the nonresonant scattering.     

Messung der Winkelverteilung der Neutronenpolarisation bei Streuung von 15,85 MeV-Neutronen am Kohlenstoff

AtE _n=15.85 MeV the angular distributions of neutron polarizationP(θ) for¹²C(n, n)¹²C and of scattering asymmetry A(θ) for¹² C(n,n′)¹² C ^*(Q=?4.43 MeV) have been measured. In a neutron time-of-flight method with a plastic scintillator as scatterer carbon recoil nuclei were used for detection. Polarized neutrons were produced in thed-t reaction atE _d=1.90 MeV at a reaction angle of 70° (lab.). WithP _n=?0.135 scattering polarizations P(θ) are forθ _lab=30, 40, 50, 60, 70, and 80° respectively ?27.0±2.1, ?48.4±2.7, ?68.7±3.6, ?20.7±6.2, +5.3±3.9, and +2.1±4.5%.     

Microwave and far-infra-red dielectric absorption inn-alkanes

Summary The power absorption coefficient (α) forn-hexane (C₆),n-heptane (C₇),n-dodecane (C₁₂) andn-tetradecane (C₁₄), benzene and cyclohexane has been studied at 20 °C, in the wave number range 20 to 300 cm⁻¹ within an accuracy of 2%. The power absorption measurements onn-alkanes (C₅−C₁₄ except for C₈, C₁₁ and C₁₃) are discussed in conjunction with the dielectric loss in the frequency range (9⋎140) GHz. The results indicate that, unlike other nonpolar liquids,n-alkanes show a broad dielectric dispersion in the microwave frequency range followed by a second dispersion in the far infra-red. The results are interpreted in terms of a dipole moment of 0.09 D in alkanes. A possible explanation for the origin of the dipole moment is discussed. A reference is also made to measurements of the dielectric loss and the Stark effect on the lower-series alkanes in the gas phase.

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Riassunto Si è studiato il coefficiente di assorbimento di potenza (α) pern-esano (C₆),n-eptano (C₇),n-dodecano (C₁₂) en-tetradecano (C₁₄), nel benzene e nel cicloensano a 20 °C nell’intervallo di numeri d’onda da 20 a 300 cm⁻¹ con un’accuratezza del 2%. Le misurazioni dell’assorbimento di potenza neglin-alcani (C₅−C₁₄, eccetto che per C₈, C₁₁ e C₁₃) sono discusse insieme alla perdita dielettrica nell’intervallo di frequenza (9⋎140) GHz. I risultati indicano che, diversamente da altri liquidi non polari, glin-alcani mostrano un’ampia dispersione dielettrica nell’intervallo di frequenza delle microonde, seguíta da una seconda dispersione nel lontano infrarosso. I risultati sono interpretati in termini di un momento dipolare di 0.09 D negli alcani. Si discute una possibile spiegazione dell’origine del momento dipolare. Si fa anche un accenno alle misurazioni della perdita dielettrica e dell’effetto di Stark sugli alcani della serie inferiore in fase gassosa.

     

Low- and medium-spin states in theN=124 isotones208Po and209At

Excited levels in²⁰⁸Po and²⁰⁹At were populated in the reactions (p, 2n) and (³He, 3n), and²⁰⁸Po also in the EC-decay of the²⁰⁸At ground state, which was produced in the²⁰⁹Bi(³He, 4n) reaction. The experimental procedures comprised gamma-ray excitation functions,γ- γ coincidences, as well as gamma-ray angular distribution and conversionelectron measurements, both on- and off-line. The properties of about twenty-five levels in each nuclide were studied. In²⁰⁸Po the energy of the 8⁺→6⁺ transition could be determined to be 4.0±0.2keV and the 8⁺ state thus has an excitation energy of 1,528 keV. The effective quadrupole charge of theh _9/2 proton can be derived ase _eff(τ h _9/2)=1.69(15)e. For the previously reported isomeric half-lives more accurate values are obtained, the systematics of electricL=1, 2 and 3 transition rates are discussed, and their microscopic structure is elucidated. Shell model considerations are used to support the configuration assignments, as are the logft values for the strongest²⁰⁸At(EC)²⁰⁸Po decay branches. The effect of core polarixation on the excitation energies of yrast states is studied in both²⁰⁸Po and²⁰⁹At. Many of the states populated in the²⁰⁸At EC decay are shown to be of core-excited character.     

Intermolecular photoinduced electron-transfer processes between C60 and aniline derivatives in benzonitrile

The quenching behavior of the triplets of C₆₀ by various aniline derivatives (1a-d and 2a-e) was investigated by means of laser flash photolysis in benzonitrile at 293 K. Electron transfer process was proposed to be the main mechanism because of the direct detection of radical ions of aniline derivatives and C₆₀ in time-resolved transient absorption spectra. The quenching rate constants (k_q) of by different substrates determined at 740 nm approach or reach the diffusion-controlled limit. DFT method was employed to calculate the unknown oxidation potentials of substrates in solution. With these E_ox values, free energy changes (ΔG) were obtained through Rehm-Weller equation. Dependence of observed quenching rate constants on the free energy changes further indicates the photoinduced reactions between ³C₆₀^* and substrates proceed through an electron transfer mechanism. Obtained k_q values for the aniline derivatives are impacted obviously by ground-state configurations and the kinds substituents quantified by Hammett σ constant. Good correlation between log k_q and σ values conforms to the empirical Hammett equation. A more negative ρ value (−3.356) was gained for anilines (2a-e) than that of N,N-dimethylanilines (1a-d) (−1.382), which suggests a more susceptible reactivity for the former substrates. Charge density distribution of reaction center “N” originated from quantum calculation supports this suggestion. In addition, a relationship between quenching rate constants and solvent viscosity was gained from C₆₀/dimethyl-p-toluidine system in altered mixtures of acetonitrile and toluene.     

The (n, 2n) excitation functions for93Nb and103Rh with special respect to the isomeric states in92Nb and102Rh

By means of the activation technique the excitation functions for the reactions⁹³Nb(n,2n)^92mNb(10.15d),¹⁰³Rh(n,2n)^102mRh(2.9y), and¹⁰³Rh(n,2n)^102gRh(206d) were measured with an average total uncertainty of about ±8% between 10 and 20 MeV neutron energy. In addition the total⁹³Nb(n, 2n) cross-section was compared with the⁵⁹Co(n, 2n) cross-section at 16.8 MeV by direct neutron detection using the time-of-flight technique. The results are compared with statistical theory, especially with theoretical expectations for the isomeric cross-section ratios, which are only in reasonable agreement with the experiment if one assumes a ground state spinI _g=5 for⁹²Nb andI _g=2 for¹⁰²Rh.     

Dielectric dispersion studies of mixtures of aniline and benzonitrile in benzene solutions

Dielectric behavior of aniline, benzonitrile and their binary mixtures of different concentrations were studied in benzene at 293, 303, 313 and 323 K. The complex permittivity (∈′, ∈″) at microwave frequencies 7.22, 9.1, 19.61 GHz, static permittivity ∈₀ at 455 KHz and high frequency limiting dielectric constant ∈_∞ = n_D² at optical frequency of these molecules and their binary mixtures were measured. The average relaxation time (τ₀), distribution parameter (α) and thermodynamical parameters were determined. The plot of relaxation time (τ₀) against concentration of benzonitrile in the mixtures is nonlinear indicating complex formation.