Spin polarization and photoinduced electron transfer between ferrocene and fullerene derivatives containing a nitroxide group

Fulleropyrroliddine derivatives containing a TEMPO group (FPNOs) are examined in toluene solution, between 200 and 270 K, by TR-EPR spectroscopy after LASER excitation. Signals of the ground and excited states are observed and their time profiles are recorded. In presence of ferrocene the time pattern of the polarization is modified, showing the occurrence of intermolecular electron transfer from the donor ferrocene to the excited FPNOs. The rate constantk _E. is obtained from the simulation of the EPR signal time evolution of the ground and excited states.     

Pair exchange interaction in a crystalline nitroxide radical ESR study of dimers in the triplet state

The dimerization of the 9-aza-bicyclo (3,3,1) nonan-3-one-9-oxyl in the solid state is investigated by use of ESR spectroscopy. The ESR spectrum of a single crystal is characteristic of symmetric pairs of exchange-coupled radicals in a thermally accessible triplet state. The presence of well-resolved hyperfine structure is evidence for strongly localized excitations with a jumping rate lower than 10⁷ Hz.

The ESR spectrum is well described by the spin hamiltonian

At 35 GHz the observed splitting of the m _s=+ 1?0 transition has been found to be slightly different from that of the m _s=0?-1 one; this anomaly is explained by the mixing of the m _s electronic states.

The parameters and the principal directions of the zero-field splitting, spectroscopic and hyperfine tensors are determined and discussed. The principal directions of the dipolar tensor indicate a nearly equal spin density on the nitrogen and oxygen atoms; from the fine structure parameters D and E, determined to be (-0·0723 ± 0·0005) cm^-1 and (-0·0044±0·0003) cm^-1 at T=293 K respectively, it is suggested that the unpaired electron is partly delocalized on the molecule.

The singlet-triplet energy gap (J) and the zero-field splitting parameters are shown to be linearly temperature-dependent. These variations with temperature are attributed to the thermal expansion of the crystal lattice.     

The sign of the exchange interaction between triplet excited fullerene and nitroxide free radicals

The sign of the exchange interactionJ in a series of radical triplet pairs (RTPs), formed by a nitroxide free radical and a triplet excited fullerene, has been determined from the spin polarization of time-resolved electron paramagnetic resonance spectra. Radical and fullerene are linked together by covalent bonds in different geometries. It is shown that the sign ofJ depends on the overlap between the orbital of nitroxide unpaired electron and the LUMO of fullerene, which is singly occupied in the excited triplet state. When the overlap does not vanish, a negative contribution toJ arises from the admixing of a charge transfer structure in the wave function of the excited doublet state D* of the RTP, which does not take place in the excited quartet state Q*. The mixing of D* and Q* states lowers the energy of the former spin state and gives antiferromagnetic coupling.     

EPR and ENDOR Study of a series of free base porphycenes in the photoexcited triplet state

Porphycene is a structural isomer of porphyrin. The photoexcited triplet states of porphycene, 2,7,12,17-tetra-n-propylporphycene and 9,10,19,20-tetra-n-propylporphycene in disordered solid solution were studied by EPR and ENDOR. The ENDOR spectra yield the hyperfine tensor elementsA _zz for each of the different groups of equivalent protons. The dipolar contribution toA _zz is estimated and spin densities are derived from the isotropic contribution. They are compared with results of all-valence-electrons self-consistent field molecular orbital calculations (RHF-INDO/SP and RHF-INDO/S).     

Electron spin polarization of doublet state species due to interaction with excited triplet states in single crystals

Doublet states species trapped in crystalline solids show transient spin polarized EPR spectra if the crystal is illuminated by visible or UV light. The spin polarization is accounted for by the interaction of the doublet species with photoexcited triplet states. The mechanism of the process producing the spin polarization is examined and some experimental examples are discussed. The analysis of the time evolution of the transient variation of the EPR signal allows the measurements of the spin lattice relaxation time and in some cases of the diffusion rate of mobile triplet excitations in the crystal lattice.     

EPR and ENDOR study of porphyrins and their covalently linked dimers in the photoexcited triplet state

The triplet states of several substituted porphyrins (Tetraphenylporphyrin (H₂TPP), Zinc-Tetramethylporphyrin (ZnTMP), Octaethylporphyrin (H₂OEP) and the Dication of H₂TPP (H₄TPP²⁺)) and two covalently linked dimers with H₂TPP-subunits in disordered solid solution were studied by EPR and ENDOR at liquid helium temperature. The measurement yields theA _zz component of the hyperfine tensors of all α-protons in the reference frame of the zero field splitting tensor. Dipolar and isotropic contributions toA _zz are discussed and spin densities derived. The spin densities are compared with results of all-valence-electrons self-consistent field molecular orbital calculations (RHF-INDO/S). One of the dimers shows indications of triplet energy transfer between the porphyrin subunits. The order of magnitude of the transfer rate is estimated to be 5 · 10⁵ s^?1.     

Peculiar spin dynamics of the photoexcited triplet state of pentacene in a benzoic acid crystal: an ESE study

The spin dynamics of the photoexcited triplet state of pentacene in three host crystals: benzoic acid, naphthalene andp-terphenyl, were measured from 5 to 300 K by the electron spin echo technique following N₂ laser excitation. The triplet kinetics (population, spinlattice relaxation and decay rates) of pentacene in the benzoic acid (BA) hosts differ from those observed in the other two host systems. A model which includes a strong guest-host interaction and proton tunneling in the tautomerization of BA hosts is used to explain the observations.     

Spin polarization of 37K produced in a single-proton pickup reaction at intermediate energies

Spin polarization of 37K nuclei produced via single proton pickup from a 9Be target by a beam of 150 MeV/nucleon 36Ar has been observed. Positive spin polarization with magnitude (8.5+/-0.6)% was deduced near the peak of the 37K momentum distribution. The variation of the spin polarization as a function of outgoing 37K momentum is explained by a classical conservation model, as previously applied to describe the induced spin polarization observed for fragments produced in intermediate-energy heavy-ion reactions, with the condition that the picked-up proton has an average momentum equal to the Fermi momentum and is aligned along the incident beam direction.     

FT-EPR study on the sign of exchange interaction in triplet naphthalene-galvinoxyl encounter pair

Chemically induced dynamic electron polarization (CIDEP) created in the quenching of triplet naphthalene by galvinoxyl were investigated by time-resolved Fourier-transform electron paramagnetic resonance (FT-EPR) measurements with monitoring a free induction decay signal of a pulsed microwave irradiation. Transient FT-EPR spectra of galvinoxyl with CIDEP were observed in various nonpolar solvents with different viscosity. A transient FT-EPR signal phase shows remarkable dependence on the viscosity: FT-EPR signal phases were absorption and emission in the solvents with low and high viscosity, respectively. Time evolutions of the FT-EPR signal of galvinoxyl were well simulated by a model of the radical-triplet pair mechanism (RTPM) for CIDEP. A sign of theJ value in the triplet naphthalene-galvinoxyl system in various solvents were discussed on the basis of the sign rule in the RTPM and the transient FT-EPR signal phase. One of possible explanation for the solvent viscosity dependence of the transient FT-EPR signal phase was pressented on the basis of hypothetical model of theJ value.     

Spin polarization dynamics and the Hanle effect for a strong exchange interaction in the exciton

The exciton spin dynamics in a quantum well with a magnetic field applied in its plane is analyzed theoretically. The exchange interaction between the electron and the hole is assumed to be strong. The width of the Hanle effect profile is shown to depend on the hole spin relaxation time. The intensity signal obtained under pulsed exciton generation as a function of time is characterized by two decay times, and the polarization signal, by a third time which is strongly dependent on the applied field.     

Magnetic field effects on the reaction of the photoexcited triplet of 2-methyl-1,4-naphthoquinone in SDS micellar solution containing the 4-(lauroylamino)-TEMPO radical

A study has ben made of magnetic field effects (MFEs) on the reaction of the photoexcited triplet of 2-methyl-1,4-naphthoquinone (MNQ) in SDS micellar solution containing the 4-lauroylamino-TEMPO radical (L-R^?) under magnetic fields below 1.75 T by a nanosecond laser flash photolysis technique. The triplet MNQ mainly underwent the hydrogen abstraction from an SDS molecule to give a radical pair. The lifetime of the radical pair increased with increasing magnetic field from 0 to 0.62 T. The escaped radical yield also increased from 0 to 1.75 T. The qualitative features of these MFEs were similar to those observed for the photo-reduction of MNQ in SDS micellar solution without L-R^?, and these MFEs can be explained by the relaxation mechanism. However, it was found that L-R^? affected the MFEs for this reaction in two ways: first, L-R^? reacted with the triplet MNQ through H abstraction and/or electron transfer, and second, the spin relaxation of the radical pair was enhanced through the spin-spin interactions of the individual radical with L-R^?.     

“Unusual” lines observed in low-frequency cw ENDOR of photoexcited triplet state molecules: the primary donor triplet in photosynthetic reaction centers as an example

The origin of frequently observed “negative” (opposite phase) ENDOR lines in the low-frequency region of triplet state ENDOR spectra is explained in terms of microwave hole burning and RF modulation phenomena. From this, a new method of detecting burnt side holes in EPR spectra is derived which is based on cw ENDOR instrumentation. The method uses the modulation satellites that are induced by a longitudinal RF field component and appear around any EPR line, including burnt holes (“negative” lines). The longitudinal RF field was generated by a coil oriented parallel to the external field, but a longitudinal component of the RF field also exists in most conventional ENDOR spectrometers because of slight misalignments of the ENDOR coil generating the transversal RF field. The lines it induces in the low-frequency part of ENDOR spectra are generally considered as artifacts. It is shown, however, that RF induced modulation satellites provide valuable information concerning the lines distant from the spectral position in the EPR spectrum chosen for ENDOR observation. This allows one to record the pattern of side holes burnt by microwave saturation through forbidden transitions that carries information about ENDOR frequencies comparable to what can be extracted from ESEEM experiments. Such comparability is demonstrated for examples of nitrogen ENDOR of photoexcited triplet states of the primary donor in photosynthetic reaction centers and related compounds.     

Excited quartet and doublet states in the complex of tetraphenylporphine zinc (II) and a nitroxide radical in solution: X- and W-band time-resolved EPR studies

The photoexcited quartet (Q₁) and doublet (D₁) states of the complex of tetra-phenyl-porphine zinc (II) and a nitroxide radical have been studied in toluene solution by X-(9.4 GHz) and W-band (94 GHz) time-resolved electron paramagnetic resonance spectroscopy. The spin-polarized signals of the Q₁ and D₁ states are observed and assigned by analysis of theg-values. Line broadening and spin polarization mechanisms in this system are discussed.     

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.     

Creation of a donor-acceptor pair for studying intraprotein electron transfer with the participation of amino-acid derivatives of fullerene C60

Efficient quenching of eosin phosphorescence by amino-acid derivatives of fullerene (AADFs) such as C₆₀-alanine and C₆₀-glycine in aqueous solutions indicates the possibility of transferring electrons from eosin to fullerene upon collisions or in the exciplex state. To investigate electron transfer in the protein structure, we studied the process of incorporation of C₆₀-alanine and C₆₀-glycine into the heme pocket of myoglobin by controlling Förster quenching. The dissociation constant for the protein-AADF complex was estimated.