Intramolecular motion and isotope effects in muonium‐substituted chloroalkyl radicals

Muon irradiation of pure liquid 3‐chloropropene, CH₂=CH-CH₂Cl, yields a primary radical, \dot\mboxCH₂-CHMu-CH₂Cl, and a secondary radical, MuCH₂-\rm\dot\mboxCH-CH₂Cl. 2‐methyl‐3‐chloropropene yields only the tertiary radical, MuCH₂-\rm\dot\mboxC(CH₃)-CH₂Cl. These three chloroalkyl radicals have been characterized by μSR and μLCR, and the hyperfine coupling constants (hfcs) have been determined over a range of temperatures, either in the pure liquid precursor or in concentrated solution. The temperature variation of the hfcs has been analyzed to obtain estimates of the barrier to internal rotation about the C_\alpha-C_\beta axis for various alkyl groups, and also their minimum energy conformations, i.e. their orientations with respect to the axis of the 2p_z orbital of the unpaired electron. The tertiary radical is particularly interesting because all three methyl‐like groups, -CH₃,-CH₂Cl and -CH₂Mu, are represented. The results can be compared to electron spin resonance data for analogous radicals, to provide information on the effects of Mu substitution for H. This revised version was published online in August 2006 with corrections to the Cover Date.     

Intramolecular dynamics in small radicals with anisotropic magnetic interactions

The ESR lineshape of one electron spin coupled by anisotropic hyperfine interaction to two nuclei is calculated when two different configurations of the molecule interchange by a simple reaction scheme. The spectrum calculation includes the anisotropic electron Zeeman interaction and the nonsecular terms of the electron spin. The lineshape, which simulates both a nonsaturated CW or a pulse experiment, is calculated numerically by using a density matrix theory within the Liouville formalism. The theory is tested against the X-band spectra of-CH₂ in ZnAc single crystal for three different orientations of the magnetic field. The present theoretical lineshape reproduces all the experimental “forbidden” transitions and predicts that they are important for certain crystal orientations. The calculated reorientation barrier of the methylene in the present work is 7.17 kcal/mol which is closer to an estimated minimum value of 9 kcal/mol, than the previous value of 5–6 kcal/mol obtained by an analysis with the modified Bloch equations.     

Hyperfine coupling constants of muonium-substituted cyclohexadienyl radicals in the gas phase: C6H6Mu, C6D6Mu, C6F6Mu

Muon spin rotation (μSR) and avoided level crossing resonance (ALCR) have been used to determine the hyperfine coupling constants (hfcs) of the muonium-substituted cyclohexadienyl radicals C₆H₆Mu, C₆D₆Mu and C₆F₆Mu in the gas phase, at pressures ～1 and 15 atm and temperatures in the range 40–80°C. Equivalent studies of polyatomic free radicals in gases, by electron spin resonance (ESR) spectroscopy, are generally not possible in this pressure range. The present gas phase results support the findings of earlier studies of cyclohexadienyl radicals in the condensed phase, by both μSR and ESR. Minor but not insignificant (～1%) effects on the hfcs are observed, which can be qualitatively understood for such nonpolar media in terms of their differing polarizabilities. This is the first time that comparisons of this nature have been possible between different phases at the same temperatures. These μSR/ALCR gas-phase results provide a valuable benchmark for computational studies on radicals, free from possible effects of solvent or matrix environments.     

Intramolecular diffusive motion in alkane monolayers studied by high-resolution quasielastic neutron scattering and molecular dynamics simulations

Molecular dynamics simulations of a tetracosane (n-C24H50) monolayer adsorbed on a graphite basal-plane surface show that there are diffusive motions associated with the creation and annihilation of gauche defects occurring on a time scale of approximately 0.1-4 ns. We present evidence that these relatively slow motions are observable by high-energy-resolution quasielastic neutron scattering (QNS) thus demonstrating QNS as a technique, complementary to nuclear magnetic resonance, for studying conformational dynamics on a nanosecond time scale in molecular monolayers.     

Intramolecular motion in the triptycenegermanyl radical: single crystal EPR study at variable temperature and DFT calculations

X-irradiation of single crystals of Tp–GeH₃ (Tp: triptycene) led to the trapping of the radical Tp–GeH₂. The angular variations of the resulting EPR spectra were recorded at 300 and 77 K. The drastic temperature dependence of the spectra was caused by both a strong anisotropy of the g-tensor and a rotation of the GeH₂ moiety around the C–Ge bond. The determination of the EPR tensors as well as the analysis of this motion required to take the presence of disorder in the crystal into account. In accordance with DFT calculations, Tp–GeH₂ is shown to be pyramidal and to adopt, in its lowest energy structure, a staggered conformation. Rotation around the C–GeH₂ bond is blocked at 90 K and is almost free above 110 K. The experimental barrier, obtained after simulation of the EPR spectra as a function of the rotational correlation time, is equal to 1.3 kcal mol⁻¹, which is slightly inferior to the barrier calculated by DFT (3.6 kcal mol⁻¹). Calculations performed on Tp–CH₃, Tp–GeH₃ and Tp–GeH₂ show that the rotation barrier ΔE_rot around the C–Ge bond drastically decreases by passing from the germane precursor to the germanyl radical and that ΔE_rot increases by passing from the germane to its carbon analogous. Structural parameters involved in these barrier differences are examined.     

Intramolecular electron transfer and charge delocalization in bistable donor–acceptor systems based on perchlorotriphenylmethyl radicals linked to ferrocene and tetrathiafulvalene units

A comparative analysis of the physicochemical properties of different donor–acceptor dyads, based on a perchlorotriphenylmethyl radical acceptor subunit linked through a vinylene π‐bridge to ferrocene derivatives (1–3) or a tetrathiafulvalene (4) donor subunit, is presented. Intramolecular electron transfer and charge delocalization of these donor–acceptor dyads are discussed on the basis of data obtained in solution by cyclic voltammetry, UV–Vis near‐infrared, and electron spin resonance spectroscopies. Bistability in the crystalline phase is also discussed on the basis of the results provided by X‐ray diffraction analysis and temperature‐dependent Mössbauer spectra. Copyright © 2014 John Wiley & Sons, Ltd.     

Intramolecular non-radiative transitions

Non-radiative electronic transitions are discussed. The probability W_i of the electron staying in the initial state i is obtained as a function of the vibrational relaxation time, in both large and small molecules. The result at low temperature is

where ε is the vibrational relaxation rate, ?ωm' is the energy difference of the levels which are involved in the transitions. An expression which depends on the phonon temperature is also obtained.     

Intramolecular hydrogen bonds in sulfur-containing aminophenols

IR Fourier spectroscopy methods have been adopted to study intramolecular interactions that occur in CCl₄ solutions of antiviral derivatives of aminophenol. Analysis of the IR spectra showed that intramolecular bonds O–H···N, O–H···O=C, N–H···O=S=O, and O–H···O=S=O can occur in these compounds depending on the substituent on the amino group. Not only the presence of intramolecular O–H···N, O–H···O=S=O, and N– H···O=S=O hydrogen bonds in 2-amino-4,6-di-tert-butylphenol derivatives containing a sulfonamide fragment but also conformational equilibrium among these types of intramolecular interactions are essential for the manifestation of high efficiency in suppressing HIV-infection in cell culture.     

Intramolecular photoinduced electron-transfer in azobenzene-perylene diimide

This paper studies the intramolecular photoinduced electron-transfer (PET) of covalent bonded azobenzene-perylene diimide (AZO-PDI) in solvents by using steady-state and time-resolved fluorescence spectroscopy together with ultrafast transient absorption spectroscopic techniques.Fast fluorescence quenching is observed when AZO-PDI is excited at characteristic wavelengths of AZO and perylene moieties.Reductive electron-transfer with transfer rate faster than 10 11 s-1 is found.This PET process is also consolidated by femtosecond transient absorption spectra.     

Intramolecular Hamiltonian logic gates

An intramolecular computing model is presented that is based on the quantum time evolution of a single molecule driven by the preparation of a non-stationary single-electron state. In our scheme, the input bits are encoded into the coupling constants of the Hamiltonian that governs the molecular quantum dynamics. The results of the computation are obtained by carrying out a quantum measurement on the molecule. We design reliable , , and logic gates. This opens new avenues for the design of more complex logic circuits at a single-molecular scale.     

Spin densities in some odd alternant radicals including linear polyene radicals

An approximate unrestricted Hartree-Fock method is used to calculate spin densities in the odd alternant radicals cyclohexadienyl, benzyl, perinaphthenyl and triphenylmethyl and the linear polyene radicals from allyl to C₁₉H₂₁. The results agree quite well with the exact calculations and with empirical estimates as well as with experimental data on hyperfine splitting constants and E.S.R. second moments.     

Nitroxide radicals

The proton hyperfine constants have been measured, using N.M.R., for a series of sterically hindered alkyl aryl nitroxides. Computer reconstructions of the electron resonance spectra show that the coupling constants obtained from the pure radical are very similar to those obtained from the electron resonance spectra of dilute solutions. Comparison of methyl and proton splittings in identical positions suggests that the radicals are σ in character although the molecular-orbital calculations are unable to distinguish between σ or π radicals.     

Intramolecular hydrogen bonds in the phenylazomethine biomolecules

The FTIR spectra of the solutions of biologically active molecules (screened phenylazomethines) in CCl₄ are studied. The role of the OH- and N=C groups in the formation of the intramolecular H bonds is analyzed. The analysis of the FTIR spectra shows that three types of H bonds (O-H…O-H, O-H…N=C, and O-H…O-H…N=C) are possible in the molecules under study. A correlation of the H-bond formation in the phenylazomethine molecules and the antivirus properties of such molecules is revealed. The antivirus activity is observed for molecules that exhibit intramolecular O-H…O-H…N=C bonds in the absence of free hydroxyls. The antivirus activity decreases when the molecule contains additional OH groups that are not involved in H bonds.     

Intramolecular TT-energy transfer in bifluorophoric laser dyes

Rates of intramolecular triplet-triplet energy transfer have been measured for three new bifluorophoric laser dyes. Strong dependence of these rates on the length of the link between the two fluorophores was observed.     

Excited State Intramolecular Proton Transfer in O-Tosylaminobenzaldehyde

Excited state intramolecular proton transfer (ESIPT) in o-tosylaminobenzaldehyde has been investigated. According to quantum-chemical calculations ESIPT in o-tosylaminobenzaldehyde is barrierless. Product of ESIPT undergoes efficient nonradiative deactivation caused by internal rotation of C(H)OH-group. The solvent orientational relaxation in anionic form of o-tosylaminobenzaldehyde was detected. The mechanism of anionic form fluorescence quenching at the addition of the base in a protic solvent is proposed. It consists in the intermolecular proton transfer from the protonated base to oxygen atom of aldehyde group followed by the internal rotation of C(H)OH-group.