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.     

TR-EPR of single and double spin-labeled C60 derivatives in frozen matrices

Time-resolved electron paramagnetic resonance spectra of two single spin-labeled and two double spin-labeled C₆₀ derivatives in frozen solution are recorded with pulsed laser excitation and 100 ns time resolution. Quartet and quintet excited species are detected which arise from the electron spin coupling of the triplet excited fullerene moiety with the unpaired spin(s) of the nitroxide label(s). Despite the similar molecular structure, in both series of single and double labeled derivatives a different behavior was found, which is due to substantial difference of the energy of exchange coupling.     

CIDEP Created by the Quenching of Photo-Excited Tryptophan at Protein Surface: A Challenge to CIDEP Probing of Protein Structural Changes

Quenching of the triplet excited state of molecular tryptophan by nitroxide radical in 1,4-dioxane and water solutions was investigated by means of time-resolved electron paramagnetic resonance (EPR) and Fourier-transform (FT)-EPR. The chemically induced dynamic electron polarization (CIDEP) signals with net emissive phase were recorded at these quenching events and were analyzed through radical-triplet pair mechanism. The CIDEP time profiles were well reproduced by Bloch and kinetic equations, assuming radical-triplet pair mechanism with the appropriate quenching rate constants. From a comparison of the simulation and the experiment, CIDEP enhancement factor in 1,4-dioxane was determined to be −30 × P _eq, where P _eq is the spin polarization of nitroxide at thermal equilibrium. Net emissive CIDEP was also observed by FT-EPR measurements on the nitroxide quenching of the triplet excited state of tryptophan residue in α-lactalbumin. Magnitude of CIDEP created in α-lactalbumin/nitroxide system depends on the pH condition of α-lactalbumin solution, which is related to protein folding dynamics. We argue the CIDEP mechanism at the α-lactalbumin surface and propose a possibility of a novel CIDEP method to probe a protein surface and structural changes.     

Influence of C60 Aggregation on Pseudorotation in the Excited Triplet State Probed by Multifrequency Time-Resolved EPR

The influence of C₆₀ aggregation on time-resolved (TR) electron paramagnetic resonance (EPR) of C₆₀ in the excited triplet state was investigated by multifrequency EPR techniques. Temperature-independent X-band (9.7 GHz) TR-EPR spectra were observed in a fresh toluene solution, while temperature-dependent ones were reported in literatures. The experimental spectra in this study indicated that the pseudorotation of pristine C₆₀ in frozen toluene solution is not frozen out even at lower temperatures. Careful investigations of TR-EPR and its decay kinetics demonstrated that the pseudorotation can be affected by C₆₀ aggregation. A comparison between X- and W-band (94.9 GHz) results indicated that the aggregation can be accelerated by a capillary effect. Three decay constants were extracted from the analysis of the decay kinetics. The fastest component was ascribed to the pseudorotation, which was independent of temperature in the range of 10–40 K. The temperature dependences of the decay kinetics showed that the pseudorotation is not affected by C₆₀ aggregation at higher temperatures.     

Dynamic electron polarization created by the radical-triplet pair mechanism: Application to the studies on excited state deactivation processes by free radicals

The radical-triplet pair mechanism for chemically induced dynamic electron polarization (CIDEP) created in the quenching of excited state molecules by free radicals is explained on the basis of recent time-resolved electron spin resonance spectroscopic results and theoretical studies. The CIDEP of 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) and galvinoxyl radicals exhibit various CIDEP patterns of net and mutliplet types and CIDEP phases of absorption and emission. The CIDEP patterns are described by the quartet-doublet state mixings within the radical-triplet encounter pairs. The mixings by the spin-dipolar and the hyperfine interactions are responsible for the net and the multiplet patterns, respectively. The factors controlling the CIDEP phases are the spin multiplicity of the excited state quenched by radicals and the sign of the intermolecular exchange interaction of the radical-triplet encounter pairs. In particular, the intermolecular charge transfer effect on the exchange interaction is discussed much in detail from the viewpoints of CIDEP magnitudes and phases. A CIDEP creation in the O₂(¹Δ_g)-TEMPO system is also introduced and is described by the radical-triplet pair mechanisms. Applications of this CIDEP used as a probe of O₂(¹Δ_g) in condensed phase are mentioned.     

Effect of charge transfer state on the exchange interaction of radical-triplet encounter pairs

Chemically induced dynamic electron polarization (CIDEP) of galvinoxyl was measured in various excited molecule-galvinoxyl systems prepared by laser photolysis. Most of the systems examined showed net emission CIDEP, which is well explained by the quartet precursor radical-triplet pair mechanism with exchange interaction,J, of negative sign (quartet is higher than doublet). Several systems with molecules such as naphthalene, quinoxaline, biphenyl and triphenylene, however, showed net absorption CIDEP. Time profiles of CIDEP and kinetic analysis of quenching suggest that net absorption CIDEP is generated during the triplet quenching process by the galvinoxyl radical. We conclude that the net absorption CIDEP is produced during the triplet quenching if theJ value of radical-triplet encounter pair is positive. This is the first report of the radical-triplet encounter pairs with positiveJ value. The mechanism for this unusual positive sign ofJ value is discussed on the basis of the spin-selective configuration interaction between the doublet spin correlated states of radical-triplet and charge transfer encounter pairs.     

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.     

Time-resolved EPR studies on magnetic interactions between excited triplet (tetraphenylporphinato) zinc and doublet nitroxide radical

By time-resolved electron paramagnetic resonance (TREPR), four (tetraphenylporphinato) zinc (ZnTPP) complexes coordinated by an axial ligand containing a nitroxide radical (NRX; X=4, 5, 8, and 10, denotes the bond number from zinc to nitroxide nitrogen) have been studied in terms of magnetic interactions between the photoexcited triplet state of ZnTPP and NRX. The TREPR spectrum of ZnTPP coordinated by NR10 is almost the same as the one of ZnTPP coordinated by pyridine, indicating that the electron exchange interaction,J, between ZnTPP and the doublet nitroxide is negligibly small. On the other hand, TREPR spectra of the NR4 and NR5 complexes are assigned to the Q₁ state constituted by the ZnTPP and the nitroxide radical. In the case of the ZnTPP-NR8 complex, both T₁ and Q₁ TREPR signals are seen, which may originate from two conformations or degenerate T₁ states of ZnTPP. This EPR study is useful for understanding the photophysical and photochemical properties of chromophores.     

Photophysical studies on axially substituted indium and gallium phthalocyanines upon UV-Vis laser irradiation

A series of results from different photophysical experiments on indium and gallium phthalocyanine (Pc) compounds is reported. Gallium Pc's have much longer singlet and triplet excited state lifetimes in comparison with indium Pc's. The strong reverse saturable absorption observed at 532 nm excitation is a consequence of the increase in absorbance of Pc's in the triplet excited state in the optical window comprised between Q- and B-bands, as verified upon laser irradiation with ns pulses at 355 nm. Using C₆₀ as a reference, the intersystem cross quantum yields of tBu₄PcInCl and tBu₄PcGaCl are 0.70 and 0.36, respectively.     

Photo-Induced Electron Transfer in P3DDT, P3OT, M3EH-PPV Conjugated Polymers Blended with Maleic Anhydride in THF Solution Under UV Flash Photolysis Studied by Means of CW TR ESR

Free-radical signals of positive polarons in conjugated polymer chains and maleic anhydride (MA) anion radicals were registered in poly(3-octylthiophene) P3OT:MA and (poly[2,5-dimethoxy-1,4-phenylene-1,2-ethenylene-2-methoxy-5-(2-ethylhexyloxy)?C(1,4-phenylene-1,2-ethenylene)]) M3EH-PPV:MA blends in tetrahydrofuran (THF) solutions under ultraviolet flash photolysis (308?nm) by continuous-wave time-resolved electron spin resonance. Their emissive chemically induced dynamic electron polarization (CIDEP) originated mainly from excited triplet states (triplet mechanism of CIDEP) and partly by from the radical pair mechanism due to the singlet?Ctriplet mixing states. The observed M3EH-PPV polaron spectrum (g ₀?=?2.0029) supports the supposition that the previously registered CIDEP spectra in P3DDT:MA blends (g ₀?=?2.0021) can be attributed to the polaron signals instead of the possible solvate electron signal one.     

Time-Resolved and Pulse EPR Study of Triplet States of Alkylketones in β-Cyclodextrin

The triplet states of deoxybenzoin (DOB) and benzophenone (BP) molecules in randomly methylated β-cyclodextrin (CD) cavity are studied by time-resolved (TR) and pulse electron paramagnetic resonance (EPR). The observed TR EPR spectrum of DOB in β-CD at 30 K is close to the spectrum measured in polar solvent trifluoroethanol, revealing strong hydration by water molecules. At the same time, TR EPR spectrum of BP in β-CD corresponds to nonpolar surrounding of the CO-group. The electron spin relaxation times T ₁ and T ₂ of triplet BP at 30 K measured by pulse EPR are found to be different in β-CD compared to nonpolar toluene glass. The observed increase of T ₂ by up to a factor of four in β-CD is caused by the lower vibration amplitude of CO-bond of BP due to the confinement in β-CD. The influence of β-CD with covalently attached nitroxide on the triplet states of DOB and BP is principally different: the excited triplet states could not be observed by TR EPR due to the efficient quenching of the excited states by nitroxide.     

Excitation dynamics of Rydberg states in C<Subscript>60</Subscript>

The electron and nuclear dynamics of C₆₀ fullerenes irradiated with femtosecond laser pulses are investigated with photoelectron and photoion spectroscopy. The focus of this work is the detailed exploration of the population mechanism of Rydberg levels within the excitation process of neutral C₆₀. The effect of excitation wavelength, intensity, chirp, and polarization on the kinetic energy distribution of photoelectrons in single-pulse experiments gives first insight into the underlying processes. In combination with time-resolved two-color pump-probe spectroscopy depending on either pump, or probe pulse intensity, a more complete picture of the interaction can be drawn. The results point towards a very interesting but nevertheless complex behavior including four steps: (i) non-adiabatic multielectron excitation of the HOMO (h_u) → LUMO+1 (t_1g) transition; (ii) thermalization within the hot electron cloud on a time scale below 100 fs, followed by a coupling of energy to vibrational modes of the molecule via doorway state(s); (iii) population of electronically excited Rydberg states by multiphoton absorption, and (iv) single photon ionization from the excited Rydberg states. This excitation process results in a characteristic sequence of photoelectron lines in the photoemission spectra. The comparison of the experimental results with recent theoretical work gives convincing evidence that non-adiabatic multielectron dynamics (NMED) plays a key role for the understanding of the response of C₆₀ to short-pulse laser radiation.     

Photoinduced intramolecular electron-transfer reactions in carbazole-fullerene and phenothiazine-fullerene linked compounds in benzene and benzonitrile as studied by fluorescence, transient absorption, time-resolved EPR, and magnetic field effects

Photoinduced intramolecular electron-transfer reactions in carbazole (Cz)-fullerene (C₆₀) (Cz(8)C₆₀) and phenothiazine (Ph)-C₆₀ (Ph(n)C₆₀ (n=8, 10, 12)) linked compounds have been investigated in benzene and benzonitrile by fluorescence, transient absorption, and time-resolved electron paramagnetic resonance measurements, and by magnetic field effects on the decay rate constants of the photogenerated biradicals. In benzonitrile, photoinduced intramolecular electron transfer from Cz to the singlet excited state of C₆₀ (¹C₆₀ ^*) occurred in Cz(8)C₆₀, but not to the triplet excited state (³C₆₀ ^*), while the intramolecular electron-transfer to both¹C₆₀ ^* and³C₆₀ ^* occurred in Ph(n)C₆₀ (n=8, 10, 12). In benzene, on the other hand, no electron transfer to both¹C₆₀ ^* and³C₆₀ ^* took place in all linked compounds. These results were interpreted in terms of the different Gibbs free energy changes in the two solvents.     

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.     

Spin polarization in fullerene derivatives containing a nitroxide group. Observation of the intermediate photoexcited quartet state in radical triplet pair interaction

A series of C₆₀ fullerene derivatives containing a nitroxide group has been photoexcited by short LASER pulses in the microwave cavity of a cw-EPR spectrometer. Strongly spin polarized signals have been observed, in glassy matrix as well as in liquid solution, for both the ground electronic state and the excited quartet state. In the quartet state the excitation resides in the fullerene part and the molecule constitutes a triplet-radical pair with the partner covalently linked. The absorptive or emissive character of the transitions is explained in terms of the mechanism of radicaltriplet interaction producing spin polarization. Opposite initial sign and polarization patterns are observed for molecules with different spacer between nitroxide and fullerene. The time evolution of the relevant sublevel populations is fitted by a kinetic model taking into account quartet decay constants, quartet and doublet spin-lattice relaxation rates and branching ratios.     

Laser-induced nonthermal fragmentation of C60 studied by semiclassical dynamics simulation

Photofragmentation of the C₆₀ fullerene induced by ultrafast laser pulses is studied by semiclassical dynamics simulation. The simulation study is focused on the excitation below the continuum levels. A laser pulse of 40 fs (FWHM) with an effective photon energy of 2.0 eV and different intensities was selected to interact with the C₆₀ fullerene. The simulation results show that averaged fragmentation size distribution over groups of initial geometries selected at random exhibits a power law pattern with the peak at C₂ at high laser pulse intensities. The threshold for the C₆₀ fragmentation was determined. The simulation finds that as many as 55 electrons are excited from the occupied molecular orbitals to unoccupied molecular orbitals upon the laser irradiation and that the number of the fragments significantly depends on the number of electrons excited. Finally, the temperature examination seems to suggest that the nonthermal effect may play a significant role in laser fragmentation of the C₆₀ fullerene.     

FT-EPR study of alkyl radicals formed in the photochemical reaction of Re(alkyl)(α-diimine) and Ru(alkyl)(α-diimine) complexes

A Fourier transform EPR (FT-EPR) study was made of the photochemistry of [Re(R)(CO)₃ (α-diimine)] and [Ru(E)(R)(CO)₂(α-diimine)] complexes, where R = alkyl or benzyl, E = I or SnPh₃, and α-diimine = 4,4′-dimethyl-2,2′-bipyridine (DMB) orN,N′-diisopropyl-1,4-diazabutadiene (iPr-DAB). Photoexcitation of these complexes leads to homolysis of the metal-alkyl (benzyl) bonds as evident from the detection of the spectra of the alkyl (benzyl) radicals. FT-EPR spectra display strong spin polarization effects attributed to Triplet Mechanism (TM) and Radical Pair Mechanism (RPM) Chemically Induced Dynamic Electron Polarization (CIDEP). CIDEP patterns point to bond dissociation via a triplet state precursor. For a number of complexes, spin polarization was found to exhibit unusually large solvent effects, whereas for one complex the CIDEP pattern proved to be sensitive to the wavelength of laser light used to initiate bond dissociation. These effects reflect the strong dependence of CIDEP on the character of the excited states involved in the photochemical reactions and contribute to the understanding of the reaction mechanism.     

EPR of photo-excited triplet states: A personal account

A sketch is presented of the path that has led from Zavoisky’s pioneering experiments to modern investigations by electron paramagnetic resonance (EPR) of the phosphorescent (S = 1) triplet state of polyatomic molecules or ions. The group-theoretical method first introduced by Wigner in his analysis of the multiplets of atomic spectroscopy, likewise provides a key for understanding the zero-field splitting and selection rules for radiative decay of the phosphorescent triplet state. Examples to illustrate the progress made through EPR experiments are selected from three fields. (i) Conformational instability on excitation. Both the zero-field splitting and the electron spin density distribution provide unique fingerprints of a triplet state’s geometry — structural information of a kind that is nonexistent for singlet states! Illustrations are provided by benzene C₆H₆ and fullerene C₆₀. (ii) The optical pumping cycle. The spin selectivity of singlet-to-triplet intersystem crossing and radiative decay of the individual spin components of the triplet state is discussed. In practice this selectivity is put to advantage by performing EPR on triplet states in zero-field by means of optical detection. In turn, such experiments have led to a detailed insight into the spin-orbit coupling mechanisms responsible for the spin selectivity of the above processes. The high sensitivity attainable with optical detection has recently culminated in EPR experiments on single molecules. (iii) Quantum interference. In a triplet state of low symmetry two of the spin sublevels may decay to the ground state by the emission of photons of a common polarization (i.e., out of plane for an aromatic hydrocarbon). In such a situation quantum interference between the two decay channels can be induced by an appropriate preparation of the excited state. An example is shown where flash-excitation in the singlet manifold followed by rapid intersystem crossing causes theS = 1 spin angular momentum to be created in a spin state which is not an eigenstate of the zero-field splitting tensor. This nonstationary character of the initial triplet state, which reflects the spin-orbit coupling pathway, is observed through the detection of a spontaneous microwave signal following the 25 ps laser flash.     

Optical limiting and pulse reshaping of picosecond pulse trains by fullerene C60

We present a dynamical theory of nonlinear absorption and propagation of a laser pulse train that contains 20 subpulses with an individual pulse width of 100 ps. It is shown that the accumulative nonlinearity and the reverse saturation absorption play important roles in the optical limiting performance and pulse shaping. When the incident field is not too strong, the population transfer reveals a slow response process, and the periodic sequence of short light pulses can be regarded as a continuous long pulse. The general theory is applied to fullerence C₆₀, which is a popular reverse saturable absorption material and a good limiter because of its larger excited-state absorption cross-section compared with that of the ground state. The propagation of the front subpulses is mainly affected by the linear transition between the ground state and the first excited singlet state, while the latter subpulses are attenuated by the excited-state absorption. Moreover, these two different kinds of absorption mechanisms result in different radial distributions for different subpulses. The pulse propagation is studied by solving numerically the coupled rate equations and the propagation equation of the optical pulse intensity, using experimental parameters as input. We suggest a new method to measure the lifetime of the triplet state.     

Electron Spin Resonance of Alkali Metal Contact Ion Pairs of 2,6-di-tert-Butylbenzoquinone in Non Polar Solvent

The question whether excited triplet states of quinones react with a number of substrates such as alcohols, phenols, and amines, via electron transfer mechanism has attracted much attention in recent years. The existence of some triplet exciplex was postulated by Kobashi et al¹ in their study of hydrogen atom abstraction by p-chloranil using laser flash spectrocopic detection. In some recent e.s.r. and CIDEP studies^2,3, however, there is no compelling evidence that the photoreduction of quinones and benzophenones undergoes an initial electron transfer mechanism. It should be noted that most of the e.s.r. studies of quinone radical anions had been carried out in polar solvents. In flash photolysis studies some evidence has indeed been obtained^1,4 in which the efficiency of hydrogen abstraction by excited triplet quinones increases with solvent polarity and therefore it is possible that the initial primary process involves electron transfer followed immediately by proton transfer. On the other hand, we