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The EPR spectra of paramagnetic species induced by photoexcitation typically exhibit enhanced absorptive and emissive features resulting from sublevel populations that differ from thermal equilibrium. The populations and the resulting spin polarization of the spectra are dictated by the selectivity of the photophysical process generating the observed state. Simulation of the spin-polarized EPR spectra is crucial in the characterization of both the dynamics of formation of the photoexcited state as well as its electronic and structural properties. EasySpin, the simulation toolbox for EPR spectroscopy, now includes extended support for the simulation of the EPR spectra of spin-polarized states of arbitrary spin multiplicity and formed by a variety of different mechanisms, including photoexcited triplet states populated by intersystem crossing, charge recombination or spin polarization transfer, spin-correlated radical pairs created by photoinduced electron transfer, triplet pairs formed by singlet fission and multiplet states arising from photoexcitation in systems containing chromophores and stable radicals. In this paper, we highlight EasySpin’s capabilities for the simulation of spin-polarized EPR spectra on the basis of illustrative examples from the literature in a variety of fields ranging across chemistry, biology, material science and quantum information science.

The enhancement and control of the electrical conductivity of organic semiconductors is fundamental for their use in optoelectronic applications and can be achieved by molecular doping, which introduces additional charge carriers through electron transfer between a dopant molecule and the organic semiconductor. Here, we use Electron Paramagnetic Resonance (EPR) spectroscopy to characterise the unpaired spins associated with the charges generated by molecular doping of the prototypical organic semiconductor poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and tris(pentafluorophenyl)borane (BCF). The EPR results reveal the P3HT radical cation as the only paramagnetic species in BCF-doped P3HT films and show evidence for increased mobility of the detected spins at high doping concentrations as well as formation of antiferromagnetically coupled spin pairs leading to decreased spin concentrations at low temperatures. The EPR signature for F4TCNQ-doped P3HT is found to be determined by spin exchange between P3HT radical cations and F4TCNQ radical anions. Results from continuous-wave and pulse EPR measurements suggest the presence of the unpaired spin on P3HT in a multitude of environments, ranging from free P3HT radical cations with similar properties to those observed in BCF-doped P3HT, to pairs of dipolar and exchange-coupled spins on P3HT and the dopant anion. Characterisation of the proton hyperfine interactions by ENDOR allowed quantification of the extent of spin delocalisation and revealed reduced delocalisation in the F4TCNQ-doped P3HT films.

The mechanism and the nature of the species formed by molecular doping of the model polymer poly(3-hexylthiophene) (P3HT) in its regioregular (rre-) and regiorandom (rra-) forms in solution are investigated for three different dopants: the prototypical π-electron acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), the strong Lewis acid tris(pentafluorophenyl)borane (BCF), and the strongly oxidizing complex molybdenum tris[1-(methoxycarbonyl)-2-(trifluoromethyl)ethane-1,2-dithiolene] (Mo(tfd-CO2Me)3). In a combined optical and electron paramagnetic resonance study, we show that the doping of rreP3HT in solution occurs by integer charge transfer, resulting in formation of P3HT radical cations (polarons) for all of the dopants considered here. Remarkably, despite the different chemical nature of the dopants and dopant–polymer interaction, the formed polarons exhibit essentially identical optical absorption spectra. The situation is very different for the doping of rraP3HT, where we observe formation of a charge-transfer complex with F4TCNQ and of a “localized” P3HT polaron on nonaggregated chains upon doping with BCF, while there is no indication of dopant-induced species in the case of Mo(tfd-CO2Me)3. We estimate the ionization efficiency of the respective dopants for the two polymers in solution and report the molar extinction coefficient spectra of the three different species. Finally, we observe increased spin delocalization in regioregular compared to regiorandom P3HT by electron nuclear double resonance, suggesting that the ability of the charge to delocalize on aggregates of planarized polymer backbones plays a significant role in determining the doping mechanism.

Doping the electron transport polymer poly [N,N amp; 8242; bis 2 octyldodecyl naphthalene 1,4,5,8 bis dicarboximide 2,6 diyl] alt 5,5 amp; 8242; 2,2 amp; 8242; bithiophene [P NDI2OD T2 ] with the bulky, strongly reducing metallocene 1,2,3,4,1 amp; 8242;,2 amp; 8242;,3 amp; 8242;,4 amp; 8242; octaphenylrhodocene OPR leads to an increased bulk conductivity and a decreased contact resistance. While the former arises from low level n doping of the intrinsic polymer and increased carrier mobility due to trap filling, the latter arises from a pronounced accumulation of dopant molecules at an indium tin oxide ITO substrate. Electron transfer from OPR to ITO leads to a work function reduction, which pins the Fermi level at the P NDI2OD T2 conduction band and thus minimizes the electron injection barrier and the contact resistance. The results demonstrate that disentangling the effects of electrode modification by the dopant and bulk doping is essential to comprehensively understand doped organic semiconductors

Electron Nuclear DOuble Resonance (ENDOR) is based on the measurement of nuclear transition frequencies through detection of changes in the polarization of electron transitions. In Davies ENDOR, the initial polarization is generated by a selective microwave inversion pulse. The rectangular inversion pulses typically used are characterized by a relatively low selectivity, with full inversion achieved only for a limited number of spin packets with small resonance offsets. With the introduction of pulse shaping to EPR, the rectangular inversion pulses can be replaced with shaped pulses with increased selectivity. Band-selective inversion pulses are characterized by almost rectangular inversion profiles, leading to full inversion for spin packets with resonance offsets within the pulse excitation bandwidth and leaving spin packets outside the excitation bandwidth largely unaffected. Here, we explore the consequences of using different band-selective amplitude-modulated pulses designed for NMR as the inversion pulse in ENDOR. We find an increased sensitivity for small hyperfine couplings compared to rectangular pulses of the same bandwidth. In echo-detected Davies-type ENDOR, finite Fourier series inversion pulses combine the advantages of increased absolute ENDOR sensitivity of short rectangular inversion pulses and increased sensitivity for small hyperfine couplings of long rectangular inversion pulses. The use of pulses with an almost rectangular frequency-domain profile also allows for increased control of the hyperfine contrast selectivity. At X-band, acquisition of echo transients as a function of radiofrequency and appropriate selection of integration windows during data processing allows efficient separation of contributions from weakly and strongly coupled nuclei in overlapping ENDOR spectra within a single experiment.

Twisting of the acene backbone out of planarity in twisted acenes leads to a variation in their optical and electronic properties. The effect of increasing twist angles on the properties of the photoexcited triplet states of a series of anthracene-based helically tethered twisted acenes is investigated here by Electron Paramagnetic Resonance (EPR) spectroscopy. Increasing signal intensities with increasing twist angles indicate increased intersystem crossing efficiencies for the twisted molecules compared to the untethered reference compound. Variations in the electron spin polarisation observed in the transient EPR spectra, in particular for the compound with the shortest tether, imply changes in the sublevel population kinetics depending on molecular geometry. Changes in the zero-field splitting parameters and in the proton hyperfine couplings for compounds with short tethers and therefore higher twist angles point towards a slight redistribution of the spin density compared to the parent compound. The experimental results can be explained by considering both an increase in twist angle and a related decrease in the dihedral angle between the phenyl side groups and the acene core. The observation of a clear excitation-wavelength dependence suggests preferential excitation of different molecular conformations, with conformers characterised by higher twist angles selected at higher wavelengths.

Fe-N-C catalysts are very promising materials for fuel cells and metal-air batteries. This work gives fundamental insights into the structural composition of an Fe-N-C catalyst and highlights the importance of an in-depth characterization. By nuclear- and electron-resonance techniques, we are able to show that even after mild pyrolysis and acid leaching, the catalyst contains considerable fractions of α-iron and, surprisingly, iron oxide. Our work makes it questionable to what extent FeN4 sites can be present in Fe-N-C catalysts prepared by pyrolysis at 900 °C and above. The simulation of the iron partial density of phonon states enables the identification of three FeN4 species in our catalyst, one of them comprising a sixfold coordination with end-on bonded oxygen as one of the axial ligands.

HYperfine Sublevel CORrElation spectroscopy (HYSCORE) is one of the most widely applied EPR techniques for the investigation of hyperfine couplings in a wide range of spin systems; here, it is applied for the first time to a photoexcited triplet state. The analytical expressions describing the electron spin echo envelope modulations in a HYSCORE experiment on a triplet state coupled to spin ½ nuclei and spin 1 nuclei with weak nuclear quadrupole interactions were derived employing the density matrix formalism and used to determine the characteristic features of this experiment when applied to a triplet state. Experimental HYSCORE spectra recorded on the photoexcited triplet state of a meso-substituted zinc porphyrin are used to investigate the 14N hyperfine interactions in this system. The results are compared to one-dimensional three-pulse Electron Spin Echo Envelope Modulation (ESEEM) experiments and the comparison clearly shows the advantage of the HYSCORE experiment for investigation of the hyperfine couplings of a spin 1 nucleus for triplet states in disordered powder samples. The experimental HYSCORE data are discussed and interpreted in light of the properties of triplet state HYSCORE spectra identified using our theoretical approach.

The radical cations of a family of π-conjugated porphyrin arrays have been investigated: linear chains of N = 1–6 porphyrins, a 6-porphyrin nanoring and a 12-porphyrin nanotube. The radical cations were generated in solution by chemical and electrochemical oxidation, and probed by vis–NIR–IR and EPR spectroscopies. The cations exhibit strong NIR bands at ∼1000 nm and 2000–5000 nm, which shift to longer wavelength with increasing oligomer length. Analysis of the NIR and IR spectra indicates that the polaron is delocalized over 2–3 porphyrin units in the linear oligomers. Some of the IR vibrational bands are strongly intensified on oxidation, and Fano-type antiresonances are observed when activated vibrations overlap with electronic transitions. The solution-phase EPR spectra of the radical cations have Gaussian lineshapes with linewidths proportional to N–0.5, demonstrating that at room temperature the spin hops rapidly over the whole chain on the time scale of the hyperfine coupling (ca. 100 ns). Direct measurement of the hyperfine couplings through electron–nuclear double resonance (ENDOR) in frozen solution (80 K) indicates distribution of the spin over 2–3 porphyrin units for all the oligomers, except the 12-porphyrin nanotube, in which the spin is spread over about 4–6 porphyrins. These experimental studies of linear and cyclic cations give a consistent picture, which is supported by DFT calculations and multiparabolic modeling with a reorganization energy of 1400–2000 cm–1 and coupling of 2000 cm–1 for charge transfer between neighboring sites, placing the system in the Robin–Day class III.

Photoexcited triplet states play a crucial role in photochemical mechanisms: long known to be of paramount importance in the study of photosynthetic reaction centres, they have more recently also been shown to play a major role in a number of applications in the field of molecular electronics. Their characterisation is crucial for an improved understanding of these processes with a particular focus on the determination of the spatial distribution of the triplet state wavefunction providing information on charge and energy transfer efficiencies. Currently, active research in this field is mostly focussed on the investigation of materials for organic photovoltaics (OPVs) and organic light emitting diodes (OLEDs). As the properties of triplet states and their spatial extent are known to have a major impact on device performance, a detailed understanding of the factors governing triplet state delocalisation is at the basis of the further development and improvement of these devices. Electron Paramagnetic Resonance (EPR) has proven a valuable tool in the study of triplet state properties and both experimental methods as well as data analysis and interpretation techniques have continuously improved over the last few decades. In this review, we discuss the theoretical and practical aspects of the investigation of triplet states and triplet state delocalisation by transient continuous wave and pulse EPR and highlight the advantages and limitations of the presently available techniques and the current trends in the field. Application of EPR in the study of triplet state delocalisation is illustrated on the example of linear multi-porphyrin chains designed as molecular wires.

Yb⋅DTMA forms a ternary complex with fluoride in aqueous solution by displacement of a bound solvent molecule from the lanthanide ion. [Yb⋅DTMA⋅F](2+) and [Yb⋅DTMA⋅OH2 ](3+) are in slow exchange on the relevant NMR timescale (

Introducing bridging ligands such as DABCO to solutions of linear zinc porphyrin oligomers has previously been shown to lead to the formation of ladder-type assemblies in which the single porphyrin units in each strand adopt a predominantly co-planar conformation. Here, we employ transient Electron Paramagnetic Resonance (EPR) to study photogenerated triplet states of these complexes in frozen solution with a particular focus on the extent of spin delocalisation. We make use of two different techniques: (i) the zero-field splitting parameters D and E are determined using transient continuous wave (cw) EPR spectroscopy and (ii) the hyperfine coupling constants, which directly reveal the extent of spin delocalisation, are quantified by orientation-selective proton Electron Nuclear DOuble Resonance (ENDOR) spectroscopy. It is found that ladder formation does not encourage triplet state delocalisation either across the bridging ligand DABCO or along the individual porphyrin strands despite their co-planar conformation, which was previously shown to allow increased electronic delocalisation.

The recent introduction of shaped pulses to Double Electron Electron Resonance (DEER) spectroscopy has led to significant enhancements in sensitivity through increased excitation bandwidths and improved control over spin dynamics. The application of DEER has so far relied on the presence of an incoherent pump channel to average out most undesired coherent effects of the pump pulse(s) on the observer spins. However, in fully coherent EPR spectrometers that are increasingly used to generate shaped pulses, the presence of coherent pump pulses means that these effects need to be explicitly considered. In this paper, we examine the effects of coherent rectangular and sech/tanh pump pulses in DEER experiments with up to three pump pulses. We show that, even in the absence of significant overlap of the observer and pump pulse excitation bandwidths, coherence transfer pathways involving both types of pulses generate spin echoes of considerable intensity. These echoes introduce artefacts, which, if not identified and removed, can easily lead to misinterpretation. We demonstrate that the observed echoes can be quantitatively modelled using a simple spin quantum dynamics approach that includes instrumental transfer functions. Based on an analysis of the echo crossing artefacts, we propose efficient phase cycling schemes for their suppression. This enables the use of advanced DEER experiments, characterized by high sensitivity and increased accuracy for long-distance measurements, on novel fully coherent EPR spectrometers.

The optoelectronic properties of conjugated porphyrin arrays render them excellent candidates for use in a variety of molecular electronic devices. Understanding the factors controlling the electron delocalization in these systems is important for further developments in this field. Here, we use transient EPR and ENDOR (Electron Nuclear Double Resonance) to study the extent of electronic delocalization in the photoexcited triplet states of a series of butadiyne-linked porphyrin oligomers. We are able to distinguish between planar and twisted arrangements of adjacent porphyrin units, as the different conformations are preferentially excited at different wavelengths in the visible range. We show that the extent of triplet state delocalization is modulated by the torsional angle between the porphyrins and therefore by the excitation wavelength. These results have implications for the design of supramolecular systems with fine-tuned excitonic interactions and for the control of charge transport.

Experimental and theoretical studies indicate that water molecules between redox partners can significantly affect their electron-transfer and possibly also the triplet-triplet energy transfer (TTET) properties when in the vicinity of chromophores. In the present work, the interaction of an intervening water molecule with the peridinin triplet state in the peridinin-chlorophyll a-protein (PCP) from Amphidinium carterae is studied by using orientation selective (2)H electron spin echo envelope modulation (ESEEM) spectroscopy, in conjunction with quantum mechanical calculations. This water molecule is located at the interface between the chlorophyll and peridinin pigments involved in the photoprotection mechanism (Chl601(602)-Per614(624), for nomenclature see reference [1]), based on TTET. The characteristic deuterium modulation pattern is observed in the electron spin-echo envelopes for the PCP complex exchanged against (2)H2O. Simulations of the time- and frequency-domain two-pulse and three-pulse ESEEM require two types of coupled (2)H. The more strongly coupled (2)H has an isotropic coupling constant (aiso) of -0.4MHz. This Fermi contact contribution for one of the two water protons and the precise geometry of the water molecule at the interface between the chlorophyll and peridinin pigments, resulting from the analysis, provide experimental evidence for direct involvement of this structured water molecule in the mechanism of TTET. The PCP antenna, characterised by a unity efficiency of the process, represents a model for future investigations on protein- and solvent-mediated TTET in the field of natural/artificial photosynthesis.

The twin-arginine translocase (Tat) carries out the remarkable process of translocating fully folded proteins across the cytoplasmic membrane of prokaryotes and the thylakoid membrane of plant chloroplasts. Tat is required for bacterial pathogenesis and for photosynthesis in plants. TatA, the protein-translocating element of the Tat system, is a small transmembrane protein that assembles into ring-like oligomers of variable size. We have determined a structural model of the Escherichia coli TatA complex in detergent solution by NMR. TatA assembly is mediated entirely by the transmembrane helix. The amphipathic helix extends outwards from the ring of transmembrane helices, permitting assembly of complexes with variable subunit numbers. Transmembrane residue Gln8 points inward, resulting in a short hydrophobic pore in the center of the complex. Simulations of the TatA complex in lipid bilayers indicate that the short transmembrane domain distorts the membrane. This finding suggests that TatA facilitates protein transport by sensitizing the membrane to transient rupture.

The dipolar interaction between two paramagnetic centres depends upon their spin–spin distance and relative orientation. Generally most experiments are carried out under conditions where the DEER signal only reports on the spin–spin distances and, for this type of data, sophisticated analysis methods for obtaining distance distributions have been developed. Recently there have been an increasing number of studies on systems where the DEER signals depend upon both distance and spin pair orientation. These investigations have relied on the use of rigid spin labels (those with a well-defined spatial position) and/or spectrometers operating at Q-band frequencies and above capable of performing DEER experiments with high resolution and sensitivity. In this article we discuss in detail orientation-selective DEER experiments for which the modulation depth and the dipolar frequencies depend on the relative orientation of the two paramagnetic centres and the distance. Analysis of the data in the presence of distance and orientation distributions is discussed, and representative examples from the literature are given for systems containing spin labels, organic cofactors, metals, and metal clusters.

Peridinin-chlorophyll-protein (PCP) complexes, where the N-terminal domain of native PCP from Amphidinium carterae has been reconstituted with different chlorophyll (Chl) species, have been investigated by time-resolved EPR in order to elucidate the details of the triplet-triplet energy transfer (TTET) mechanism. This spectroscopic approach exploits the concept of spin conservation during TTET, which leads to recognizable spin-polarization effects in the observed time-resolved EPR spectra. The spin polarization produced at the acceptor site (peridinin) depends on the initial polarization of the donor (chlorophyll) and on the relative geometric arrangement of the donor-acceptor spin axes. A variation of the donor triplet state properties in terms of population probabilities or triplet spin axis directions, as produced by replacement of chlorophyll a (Chl a) with non-native chlorophyll species (ZnChl a and BacterioChl a) in the reconstituted complexes, is unambiguously reflected in the polarization pattern of the carotenoid triplet state. For the first time, in the present investigation spin-polarization conservation has been shown to occur among natural cofactors in protein complexes during the TTET process. Proving the validity of the assumption of spin conservation adopted in the EPR spectral analysis, the results reinforce the hypothesis that in PCP proteins peridinin 614, according to X-ray nomenclature (Hofmann, E.; et al. Science 1996, 272, 1788-1791), is the carotenoid of election in the photoprotection mechanism based on TTET.