Yuri E. Kandrashkin

Redox control of photoinduced electron transfer in axial terpyridoxy porphyrin complexes.

The photophysical properties of axial-bonding types (terpyridoxy)aluminum(III) porphyrin (Al(PTP)), bis(terpyridoxy)tin(IV) porphyrin (Sn(PTP) 2), and bis(terpyridoxy)phosphorus(V) porphyrin ([P(PTP) 2] (+)) are reported. Compared with their hydroxy analogues, the fluorescence quantum yields and singlet-state lifetimes were found to be lower for Sn(PTP) 2 and [P(PTP) 2] (+), whereas no difference was observed for Al(PTP). At low temperature, all of the compounds show spin-polarized transient electron paramagnetic resonance (TREPR) spectra that are assigned to the lowest excited triplet state of the porphyrin populated by intersystem crossing. In contrast, at room temperature, a triplet radical-pair spectrum that decays to the porphyrin triplet state with a lifetime of 175 ns is observed for [P(PTP) 2] (+), whereas no spin-polarized TREPR spectrum is found for Sn(PTP) 2 and only the porphyrin triplet populated by intersystem crossing is seen for Al(PTP). These results clarify the role of the internal molecular structure and the reduction potential for electron transfer from the terpyridine ligand to the excited porphyrin. It is argued that the efficiency of this process is dependent on the oxidation state of the metal/metalloid present in the porphyrin and the reorganization energy of the solvent.

A new approach to determining the geometry of weakly coupled radical pairs from their electron spin polarization patterns.

Analytical expressions for the spin polarized EPR lineshapes of weakly coupled radical pairs (RPs) are derived as functions of the angles between the anisotropic g-tensors of the radicals and the vector describing the dipolar coupling. It is shown that with a singlet precursor the EPR signal of the RP can be written as a linear function of the dipolar coupling. Under these conditions, the calculated powder spectrum can be expressed as a linear combination of four powder spectra, which are independent of the geometry of the RP. To reproduce the experimental spectra the optimal set of coefficients can be found by least-squares fitting. The advantage of this approach is that the four powder spectra must only be calculated once. This treatment shows very clearly the restrictions placed on the information obtainable from such spectra. Most importantly, a unique set of angles can only be obtained if the absolute amplitude of the spectrum is known. In general, the calculated spectrum is related to the experimental spectrum by an unknown, arbitrary scaling factor. In this case, sets of angles consistent with the data are obtained. Possible strategies for obtaining unique geometric information are discussed and demonstrated with the experimental data for the state P+*(865)Q-*(A) in Zn-substituted bacterial reaction centres.

Time-resolved EPR spectroscopy of photosynthetic reaction centers: from theory to experiment

A theoretical description of the electron spin polarization in sequential radical pairs generated by light-induced electron transfer is reviewed and several examples of its application to experimental time-resolved electron paramagnetic resonance from photosynthetic reaction centers are given. It is shown that most of the features of the observed spectra can be understood in terms of basic properties of the radical paris. The most crucial aspect used in the analysis is that the polarization of the observed radical pairs predominantly inherits the singlet character of the initial excited state of the primary donor. The motion of the spins also generates a small amount of additional polarization during the course of the sequential electron transfer. The theory provides a simple set of rules for qualitative interpretation of experimental data as well as a mathematical model for quantitative simulations of spectra. The comparison of simulated and experimental spectra demonstrates excellent agreement.

Novel intramolecular electron transfer in axial bis(terpyridoxy)phosphorus(V) porphyrin studied by time-resolved EPR spectroscopy

Laser flash-induced spin-polarized transient electron paramagnetic resonance (TREPR) spectra for bis(terpyridoxy)phosphorus(V) porphyrin in a nematic liquid crystal isotropic and in frozen solution are presented. At room temperature, two sequential spin-polarized TREPR spectra are observed. The first is consistent with the triplet state of a radical pair, while the later is assigned to the triplet state of the porphyrin formed by charge recombination. On the basis of the spectroscopic and redox properties of the terpyridine and porphyrin moieties it is proposed that electron transfer from the terpyridine to the excited phosphorus(V) porphyrin occurs. The lifetime of the radical pair is estimated to be of about 175 ns. At low temperature, the radical pair spectrumis no longer observed and the spin polarization pattern of the porphyrin triplet is dramatically different. This behavior is explained by postulating that the electron transfer is inhibited at low temperature because molecular motion is required to stabilize the radical pair. It is proposed that in the absence of this stabilization, the porphyrin triplet state is populated via spin-orbit coupling-mediated intersystem crossing from the excited singlet state.

Electron spin polarization of the excited quartet state of strongly coupled triplet-doublet spin systems.

The electron spin polarization associated with electronic relaxation in molecules with trip-quartet and trip-doublet excited states is calculated. Such molecules typically relax to the lowest trip-quartet state via intersystem crossing from the trip doublet, and it is shown that when spin-orbit coupling provides the main mechanism for this relaxation pathway it leads to spin polarization of the trip quartet. Analytical expressions for this polarization are derived using first- and second-order perturbation theory and are used to calculate powder spectra for typical sets of magnetic parameters. It is shown that both net and multiplet contributions to the polarization occur and that these can be separated in the spectrum as a result of the different orientation dependences of the +/-1/2<-->+/-3/2 and +1/2<-->-1/2 transitions. The net polarization is found to be localized primarily in the center of the spectrum, while the multiplet contribution dominates in the outer wings. Despite the fact that the multiplet polarization is much stronger than the net polarization for individual orientations of the spin system, the difference in orientation dependence of the transitions leads to comparable amplitudes for the two contributions in the powder spectrum. The influence of this difference on the line shape is investigated in simulations of partially ordered samples. Because the initial nonpolarized state of the spin system is not conserved for the proposed mechanism, the net polarization can survive in the doublet ground state following electronic relaxation of the triplet part of the system.

Light-induced electron spin polarization in the ground state of water-soluble copper porphyrins

Light-induced spin-polarized transient EPR spectra are reported for several water-soluble copper porphyrins. The spectra are assigned to the doublet ground state, with emissive spin polarization resulting from photoexcitation and subsequent electronic relaxation. In contrast to other systems for which polarization of a doublet ground state has been observed, the exchange interactions in the copper porphyrins are strong and the geometry is fixed. It is proposed that intersystem crossing from the photoexcited trip-doublet to the trip-quartet state can lead to net polarization of the spin system and that this polarization is maintained during electronic decay, possibly via charge-transfer and exciplex states. The intensity of the observed spin polarization is essentially independent of the molecular orientation in the external field, but is strongly dependent on the nature of the charged peripheral groups. Possible reasons for this behavior are discussed.

Observation of a photoexcited state of a paramagnetic transition metal complex by time-resolved electron paramagnetic resonance spectroscopy

The first observation of a spin polarized excited state of a paramagnetic metal-complex using time-resolved electron paramagnetic resonance (TREPR) spectroscopy is reported for octaethylporphinatooxovanadium(iv). The TREPR spectra show well resolved orientation dependent hyperfine splitting to the I = 7/2 vanadium nucleus. The reduction of the hyperfine splitting by a factor of 3 compared to the ground state and the observation of a multiplet pattern of spin polarization allow the TREPR spectra to be assigned to the excited quartet state of the complex. The spin polarization patterns evolve with time and it is postulated that this is a result of the equilibration between the lowest excited quartet and doublet states.

A Transient EPR Study of Electron Transfer in Tetrathiafulvalene-Aluminum(III) Porphyrin-Anthraquinone Supramolecular Triads

Abstract The stabilization of light-induced charge separation in two axially bound triads based on aluminum(III) porphyrin (AlPor) are investigated using the electron spin polarization patterns of the final radical pair state. In the triads, TTF-(Ph)n-py-AlPor-AQ, (n=0, 1) anthraquinone (AQ) is attached covalently to the Al(III) center, while the donor tetrathiafulvalene (TTF) coordinates to Al(III) on the opposite face of the porphyrin ring via the appended pyridine (py). The dyad AlPor-AQ has been studied previously (M. Kanematsu, P. Naumov, T. Kojima, S. Fukuzumi, Chem. Eur. J. 17 (2011) 12372.) and shown to undergo fast light-induced charge separation and triplet recombination. Here, it is shown that by coordinating pyridine-appended TTF to the porphyrin, the charge separation can be stabilized. The spin polarized transient EPR spectra of the state TTF·+AQ·− can be observed in both the glass phase and in liquid solution and show that the state is formed from a singlet precursor on a timescale of less than ~0.5 ns. Using structural models to fix the geometry of the radical pair and the strength of the dipolar coupling, it is possible to determine the sign and approximate magnitude of the exchange coupling between TTF·+ and AQ·−. In contrast, other similar triads, which display relatively large ferromagnetic coupling, the exchange coupling is found to be small and antiferromagnetic. This difference can be rationalized as a result of differences in the structure of the bridge between the porphyrin and the acceptor.