Triplet Radical Pair Research Articles

Analytical model for spin dynamics in radical pairs under the spin-locking condition.

Spin dynamics in triplet radical pairs are theoretically studied under the spin-locking condition, where singlet-triplet mixing is blocked by the resonant microwave field. A key assumption in the theory is simultaneous excitations of T+-T0 and T--T0 transitions in triplet radical pairs. This assumption allows for the application of a three-state model [Yago, J. Chem. Phys. 151, 214501 (2019)] to describe the spin dynamics of triplet radical pairs. The analysis based on the three-state model shows that the triplet states are quantized along the direction of a microwave-induced magnetic field (B1) in the rotating frame under the spin-locking condition. This gives rise to a new spin-locking phenomenon where T+-T0 and T--T0 mixing are most enhanced at magnetic fields that deviate from the resonance by ±B1. It is also shown that the quantum beats observed under the spin-locking condition originate from the spin dynamics in triplet radical pairs.

Fast photochromism of helicene-bridged imidazole dimers.

The unique optical and magnetic properties of organic biradicaloids on polycyclic aromatic hydrocarbons are of fundamental interest in the development of novel organic optoelectronic materials. Open-shell π-conjugated molecules with helicity have recently attracted a great deal of attention due to the magnetic-field-dependence and spin-selectivity arising from the combination of helical chirality and electron spins. However, the molecular design for helical biradicaloids is limited due to the thermal instability and high reactivity. Herein, we achieved fast photochromic reactions and reversible photo-generation of biradical species using helicene-bridged imidazole dimers. A [9]helicene-bridged imidazole dimer exhibits reversible photochromism upon UV light irradiation. The transient species produced reversibly by UV light irradiation exhibited ESR spectra with a fine structure characteristic of a triplet radical pair, indicating the reversible generation of the biradical. The half-life of the thermal recombination reaction of the biradical was estimated to be 29 ms at 298 K. Conversely, a substantial activation energy barrier was confirmed for the intramolecular recombination reaction in the [7]helicene-bridged imidazole dimer, attributed to the extended pitch length of [7]helicene. The temperature dependence of the thermal back reactions revealed that the [7]helicene and [9]helicene moieties functioned as 'soft' and 'hard' molecular bridges, respectively. These findings pave the way for future advances in the development of photoswitchable helical biradicaloids.

Exceptionally Long Lifetimes of Strongly Entangled Acyl–Trityl Radical Pairs Photochemically Generated in Crystalline Trityl Ketones

Triplet acyl-alkyl radical pairs generated by pulsed laser excitation within the constraints of their nanocrystalline ketone precursors were recently introduced as a potential platform for the robust and repeated instantiation of spin qubit pairs for applications in quantum information science. Here, we report the transient spectroscopy of a series of nanocrystalline trityl-alkyl and trityl-aryl ketones capable of generating correlated triplet radical pairs with persistent triphenylmethyl radicals forced to remain within bonding distances of highly reactive acyl radicals. Whereas triplet trityl-acyl radical pairs decay by competing product-forming decarbonylation and intersystem crossing, triplet trityl-benzoyl radical pairs have lifetimes of up to ca. 4 ms and exclusively regenerate the starting ketone. We propose that these long lifetimes are the result of the short inter-radical distances and the colinear orientation of the two singly occupied orbitals, which are expected to result in large singlet-triplet energy gaps, large zero-field splitting parameters, and a poor geometry for spin-obit coupling. Ketones generating trityl-benzoyl radical pairs demonstrate promising performance along multiple dimensions that are crucial for quantum information science.

Sample volume effects in optical overhauser dynamic nuclear polarization

The optical dynamic nuclear polarization (DNP) method has been proposed as an alternative to microwave pumping as a hyperpolarization method for solution-state NMR studies. Using continuous laser illumination to photogenerate triplet states in the presence of a persistent radical produces chemically-induced dynamic electron polarization (CIDEP) via the radical-triplet pair mechanism (RTPM), with cross-relaxation transferring this to nuclear hyperpolarization via an Overhauser mechanism. Numerical simulations have previously indicated that reducing the sample volume while maintaining a constant optical density can significantly increase the NMR signal enhancement, due to the larger steady-state concentration of triplets obtained. Here we provide the first experimental confirmation of these effects, producing a nearly five-fold increase in the optical DNP enhancement factor just by reducing the sample volume with optimal dye and radical concentrations adjusted for each optical path length. The results are supported with an in depth analysis of volume effects in the numerical model, with which they are in good qualitative agreement. These important observations will impact on the future development of the technique, with particular significance for attempts to apply DNP methods to increase sensitivity for volume-limited biological samples.

Strongly Entangled Triplet Acyl-Alkyl Radical Pairs in Crystals of Photostable Diphenylmethyl Adamantyl Ketones.

Radical pairs generated in crystalline solids by bond cleavage reactions of triplet ketones offer the unique opportunity to explore a frontier of spin dynamics where rigid radicals are highly entangled as the result of short inter-radical distances, large singlet-triplet energy gaps (ΔEST), and limited spin-lattice relaxation mechanisms. Here we report the pulsed laser generation and detection of strongly entangled triplet acyl-alkyl radical pairs generated in nanocrystalline suspensions of 1,1-diphenylmethyl 2-ketones with various 3-admantyl substituents. The sought-after triplet acyl-alkyl radical pairs could be studied for the first time in the solid state by taking advantage of the efficient triplet excited state α-cleavage reactions of 1,1-diphenylmethyl ketones and the slow rate of CO loss from the acyl radicals, which would have to generate highly unstable phenyl and primary alkyl radicals or relatively unstable secondary and tertiary alkyl radicals. With the loss of CO prevented, the lifetime of the triplet acyl-alkyl radical pair intermediates is determined by intersystem crossing to the singlet radical pair state, which is followed by immediate bond formation to the ground state starting ketone. Experimental results revealed biexponential kinetics with long-lived components that account for ca. 87-92% of the transient population and lifetimes that extend to the range of 53-63 μs, the longest reported so far for this type of radical pair. Structural information inferred from the starting ketone will make it possible to analyze the affects of proximity and orientation of the singly occupied orbitals and potentially help set a path for the use of triplet radical pairs as qubits in quantum information technologies.

From Incident Light to Persistent and Regenerable Radicals of Urea-Assembled Benzophenone Frameworks: A Structural Investigation.

Herein we probe the effects of crystalline structure and geometry on benzophenone photophysics, self-quenching, and the regenerable formation of persistent triplet radical pairs at room temperature. Radical pairs are not observed in solution but appear via an emergent pathway within the solid-state assembly. Single crystal X-ray diffraction (SC-XRD) of two sets of constitutional isomers, benzophenone bis-urea macrocycles, and methylene urea-tethered dibenzophenones are compared. Upon irradiation with 365 nm light-emitting diodes (LEDs), each forms photogenerated radicals as monitored by electron paramagnetic resonance (EPR). Once generated, the radicals exhibit half-lives from 2 to 60 days before returning to starting material without degradation. Re-exposure to light regenerates the radicals with similar efficiency. Subtle differences in the structure of the crystalline frameworks modulates the maximum concentration of photogenerated radicals, phosphorescence quantum efficiency (φ), and n-type self-quenching as observed using laser flash photolysis (LFP). These studies along with the electronic structure analysis based on the time-dependent density functional theory (TD-DFT) suggest the microenvironment surrounding benzophenone largely dictates the favorability of self-quenching or radical formation and affords insights into structure/function correlations. Advances in understanding how structure determines the excited state pathway solid-state materials undertake will aid in the design of new radical initiators, components of OLEDs, and NMR polarizing agents.

Optically-generated Overhauser dynamic nuclear polarization: A numerical analysis.

Recently, an alternative approach to dynamic nuclear polarization (DNP) in the liquid state was introduced using optical illumination instead of microwave pumping. By exciting a suitable dye to the triplet state which undergoes a diffusive encounter with a persistent radical forming a quartet-doublet pair in the encounter complex, dynamic electron polarization (DEP) is generated via the radical-triplet pair mechanism. Subsequent cross-relaxation generates nuclear polarization without the need for microwave saturation of the electronic transitions. Here, we present a theoretical justification for the initial experimental results by means of numerical simulations. These allow investigation of the effects of various experimental parameters, such as radical and dye concentrations, sample geometry, and laser power, on the DNP enhancement factors, providing targets for experimental optimization. It is predicted that reducing the sample volume will result in larger enhancements by permitting a higher concentration of triplets in a sample of increased optical density. We also explore the effects of the pulsed laser rather than continuous-wave illumination, rationalizing the failure to observe the optical DNP effect under illumination conditions common to DEP experiments. Examining the influence of the illumination duty cycle, the conditions necessary to permit the use of pulsed illumination without compromising signal enhancement are determined, which may reduce undesirable laser heating effects. This first simulation of the optical DNP method therefore underpins the further development of the technology.

Ketyl-phenoxyl triplet radical pair in glycerol: Magnetic field effect and cage kinetics in terms of the two-state model.

The geminate recombination kinetics of the triplet pairs of neutral radicals formed as a result of hydrogen atom transfer from 4-methylphenol to 4,4'-dimethylbenzophenone in the triplet excited state was studied by laser flash photolysis in the temperature range of 263-323 K. The pair included aromatic ketyl and 4-methylphenoxyl radicals produced in a viscous (∼10 P) solution of the initial reagents in glycerol. The geminate recombination kinetics demonstrate a "tail" c(t) ∼ 1/t, with contribution of magnitude An, which increases with temperature. The two-state (TS) model, which takes into account the potential well caused by the interaction between radicals at short distances and the radicals that escaped from a well but returned to it after free diffusion outside the well, was used to fit the data. The application of an external magnetic field (MF) (0.2 T) gave rise to the retardation of the geminate recombination and to the increase of fraction of radicals in the solvent bulk. The bell-shaped dependence of the magnetic field effect (MFE) value upon temperature (with a maximum near 300 K) was found. This dependence correlates with An and its dependence on the MF. At temperatures lower than 270 K, both the contribution of the nonexponential part of geminate recombination kinetics and the MFE were found to be small. The TS model can quantitatively describe the effects of solvent viscosity and MF on the kinetics of geminate recombination of triplet RP.

A phenomenological scheme for reversed quartet mechanism of electron spin polarization in covalently linked systems of chromophore and free radical: Determination of magnitude of polarization and application to pyrene-TEMPO linked molecules.

Generation of electron spin polarization (ESP) during the bimolecular quenching of an excited chromophore by a free radical is generally explained by the radical-triplet pair mechanism, which is capable of giving the magnitudes of ESP arising from the quenching of the singlet or the triplet excited chromophore. When the chromophore and the free radical are covalently linked, although there are several mechanisms to explain the observed spin-polarized electron paramagnetic resonance signals under a variety of experimental conditions and in different chromophore-radical systems, there are no schemes that allow quantitative determination of the magnitude of ESP. In this work, we present a phenomenological scheme with this objective. In this scheme, we have incorporated several concepts of the reversed quartet mechanism of Rozenshtein et al. [J. Phys. Chem. A 109, 11144 (2005)] to our phenomenological sequential quenching scheme [V. Rane and R. Das, J. Phys. Chem. A 119, 5515 (2015)] of ESP in covalently linked chromophore-radical systems. This phenomenological reversed quartet scheme is able to explain the observed inversion of ESP with time and can also give a quantitative measure of the absorptive and emissive ESP in such systems. We have applied this scheme to the photophysical quenching of a series of newly synthesized pyrene-TEMPO molecules, where a spacer group of different lengths covalently links the pyrene chromophore and the TEMPO free radical. Given the simplicity of our scheme, reasonable estimates of the magnitudes of the ESP have been obtained in all cases.

Studies on coherent and incoherent spin dynamics that control the magnetic field effect on photogenerated radical pairs

Since 1970s, magnetic field effects (MFEs) on photogenerated radical pairs have been the centre of focus in the field of spin chemistry. The MFE attributes to quantum mechanical interconversion between the singlet and triplet radical pair states and subsequent spin-selective recombination reactions. In this New View article, the author picks up two hot topics studied during the last two decades, which are (i) so-called low field effect (LFE) and (ii) 2J-resonance MFE on fixed distance donor–acceptor linked molecules. In both of the topics, quantum mechanical explanations are given referring to recent reports, and some novel calculations have been carried out for bridging theoretical and experimental data for long-lived radical pairs. For the first topic, time domain calculations of coherent state mixing have been carried out for elucidation of hyperfine (HF) structure dependence of the LFE. For the second topic, Monte Carlo simulations of the torsional motion of polyaromatic linker unit have been carried out for the demonstration of fast decoherence in such rigid molecules. From these considerations, future possibilities of MFE studies on photo-functional materials and biomolecules have been indicated.

Toward Achieving the Theoretical Limit of Electron Spin Polarization in Covalently Linked Radical-Chromophore Dyads.

Electron spin systems with non-Boltzmann spin distributions are commonly observed in photophysical and photochemical processes involving free radicals. Understanding the origin of electron spin polarization (ESP) reveals detailed insight into the spin-dependent interactions occurring in these processes. The ability to transfer ESP to the nuclear spins of the solvent to produce large nuclear polarization is itself an active area of research in the field called dynamic nuclear polarization (DNP). Harnessing ESP in such fields demands a large magnitude of ESP and importantly on free radicals that are stable. In this work, we explored various factors that could play a prominent role in generation of ESP on the stable nitroxyl radical. By exploiting the dependence of ESP on the zero-field splitting parameter DT of the chromophore triplets and a careful choice of the chromophores for efficient quenching of their excited states by a free radical, we present here our strategies for designing covalently linked chromophore-free radical dyads, which could generate high magnitudes of ESP. Syntheses and EPR studies on a series of such dyads to demonstrate successful realization of our strategy are reported here. Our work reveals that, along with the DT value and the triplet quenching efficiency, the relative orientational dynamics of the radical and chromophore moiety and an efficient intersystem crossing of the chromophore primarily govern the ESP of the chromophore-radical dyads. One such molecule, an anthraquinone moiety linked to a TEMPO free radical that optimally satisfies the above criteria, produces a very large value of ESP-about 300 times its Boltzmann value-reaching almost half of the theoretical maximum of the radical-triplet pair mechanism of ESP. Coupled with its excellent photostability in benzene and the use of ambient conditions, this molecule should prove to be highly desirable in photoinduced DNP studies and other applications such as highly sensitive magnetometers, which require generation of large nuclear spin polarization in the solvent by transferring the electron spin polarization.

Photochemical Spin Dynamics of the Vitamin B12 Derivative, Methylcobalamin.

Derivatives of vitamin B12 are six-coordinate cobalt corrinoids found in humans, other animals, and microorganisms. By acting as enzymatic cofactors and photoreceptor chromophores, they serve vital metabolic and photoprotective functions. Depending on the context, the chemical mechanisms of the biologically active derivatives of B12-methylcobalamin (MeCbl) and 5'-deoxyadenosylcobalamin (AdoCbl)-can be very different from one another. The extent to which this chemistry is tuned by the upper axial ligand, however, is not yet clear. Here, we have used a combination of time-resolved Fourier transform-electron paramagnetic resonance (FT-EPR), magnetic field effect experiments, and spin dynamic simulations to reveal that the upper axial ligand alone only results in relatively minor changes to the photochemical spin dynamics of B12. By studying the photolysis of MeCbl, we find that, similar to AdoCbl, the initial (or "geminate") radical pairs (RPs) are born predominantly in the singlet spin state and thus originate from singlet excited-state precursors. This is in contrast to the triplet RPs and precursors proposed previously. Unlike AdoCbl, the extent of geminate recombination is limited following MeCbl photolysis, resulting in significant distortions to the FT-EPR signal caused by polarization from spin-correlated methyl-methyl radical "f-pairs" formed following rapid diffusion. Despite the photophysical mechanism that precedes photolysis of MeCbl showing wavelength dependence, the subsequent spin dynamics appear to be largely independent of excitation wavelength, again similar to AdoCbl. Our data finally provide clarity to what in the literature to date has been a confused and contradictory picture. We conclude that, although the upper axial position of MeCbl and AdoCbl does impact their reactivity to some extent, the remarkable biochemical diversity of these fascinating molecules is most likely a result of tuning by their protein environment.

Enhancing the Stability of Photogenerated Benzophenone Triplet Radical Pairs through Supramolecular Assembly.

Supramolecular assembly of urea-tethered benzophenone molecules results in the formation of remarkably persistent triplet radical pairs upon UV irradiation at room temperature, whereas no radicals were observed in solution. The factors that lead to emergent organic radicals are correlated with the microenvironment around the benzophenone carbonyl, types of proximal hydrogens, and the rigid supramolecular network. The absorption spectra of the linear analogues were rationalized using time-dependent density functional theory calculations on the crystal structure and in dimethyl sulfoxide, employing an implicit solvation model to describe structural and electronic solvent effects. Inspection of the natural transition orbitals for the more important excitation bands of the absorption spectra indicates that crystallization of the benzophenone-containing molecules should present a stark contrast in photophysical properties versus that in solution, which was indeed reflected by their quantum efficiencies upon solid-state assembly. Persistent organic radicals have prospective applications ranging from organic light-emitting diode technology to NMR polarizing agents.

Large Magneto-Current Effect in the Electrochemical Detection of Oxalate in Aqueous Solution

Herein, we first report an interesting observation of a large magneto-current (MC) of nearly 30% based on the electrochemical oxidation of oxalate in aqueous solution at room temperature. The large MC is ascribed to spin-dependent oxidation of oxalate. Both singlet and triplet radical pairs are generated during the electrochemical oxidation of oxalate. An applied magnetic field could accelerate the spin evolution of a singlet radical pair into its triplet state. The triplet radical pair has a much larger dissociation probability than the singlet radical pair because of the Pauli exclusion principle. Thus, enhancing the triplet yield could largely increase the oxidation rate of oxalate and generate significant MC. The significant MC effect provides a new approach to study spin evolution of radical pairs in electrochemical cells. Furthermore, an effective analytical method for oxalate determination can be developed based on the significant MC effect.

Transient Kinetics and Quantum Yield Studies of Nanocrystalline α-Phenyl-Substituted Ketones: Sorting Out Reactions from Singlet and Triplet Excited States.

Recent work has shown that diarylmethyl radicals generated by pulsed laser excitation in nanocrystalline (NC) suspensions of tetraarylacetones constitute a valuable probe for the detailed mechanistic analysis of the solid-state photodecarbonylation reaction. Using a combination of reaction quantum yields and laser flash photolysis in nanocrystalline suspensions of ketones with different substituents on one of the α-carbons, we are able to suggest with confidence that a significant fraction of the initial α-cleavage reaction takes place from the ketone singlet excited state, that the originally formed diarylmethyl-acyl radical pair loses CO in the crystal with time constants in the sub-nanosecond regime, and that the secondary bis(diarylmethyl) triplet radical pair has a lifetime limited by the rate of intersystem crossing of ca. 70 ns.

Accessibility of Protein-Bound Chlorophylls Probed by Dynamic Electron Polarization.

The possibility to probe the accessibility of sites of proteins represents an important point to explore their interactions with specific substrates in solution. The dynamic electron polarization of nitroxide radicals induced by excited triplet states of organic molecules is a phenomenon that is known to occur in aqueous solutions. The interaction within the radical-triplet pair causes a net emissive dynamic electron polarization of the nitroxide radical, that can be detected by means of time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy. We have exploited this effect to prove the accessibility of chlorophylls bound to a protein, namely, the water-soluble chlorophyll protein WSCP. The results have important implications for topological studies in macromolecules.

Generating Huge Magnetocurrent by Using Spin-Dependent Dehydrogenation Based on Electrochemical System

Systems featuring large magnetocurrent (MC) at room temperature are attractive owing to their potential for application in magnetic field sensing. Usually, the magnetic materials are exploited to achieve large MC effect. Here, we report a huge MC of up to 150% in a nonmagnetic system based on the electrochemical oxidation of hydrazine at room temperature. The huge MC is ascribed to the spin-dependent N–H bond cleavage and reformation through dehydrogenation during the oxidation of hydrazine. Specifically, the N–H bond cleavage generates singlet radical pairs. An external magnetic field can accelerate the spin evolution from singlet to triplet in spin-correlated radical pairs by perturbing spin precessions. Increasing the amount of triplet radical pairs can largely reduce the N–H bond recovery and significantly enhance the oxidation current of hydrazine. As a consequence, the spin-dependent bond formation through dehydrogenation can provide a new approach to generate huge MC in electrochemical cells.

Formation of singlet oxygen by decomposition of protein hydroperoxide in photosystem II.

Singlet oxygen (1O2) is formed by triplet-triplet energy transfer from triplet chlorophyll to O2 via Type II photosensitization reaction in photosystem II (PSII). Formation of triplet chlorophyll is associated with the change in spin state of the excited electron and recombination of triplet radical pair in the PSII antenna complex and reaction center, respectively. Here, we have provided evidence for the formation of 1O2 by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. Protein hydroperoxide is formed by protein oxidation initiated by highly oxidizing chlorophyll cation radical and hydroxyl radical formed by Type I photosensitization reaction. Under highly oxidizing conditions, protein hydroperoxide is oxidized to protein peroxyl radical which either cyclizes to dioxetane or recombines with another protein peroxyl radical to tetroxide. These highly unstable intermediates decompose to triplet carbonyls which transfer energy to O2 forming 1O2. Data presented in this study show for the first time that 1O2 is formed by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex.

Radical-Enhanced Intersystem Crossing in New Bodipy Derivatives and Application for Efficient Triplet-Triplet Annihilation Upconversion.

A long-lived triplet excited state of the well-known fluorophore boron dipyrromethene (Bodipy) was observed for the first time via efficient radical-enhanced intersystem crossing (EISC). The triplet state has been obtained in two dyads in which the Bodipy unit is linked to a nitroxide radical, 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO), with two different length spacers. The photophysical properties were studied with steady-state and time-resolved transient optical spectroscopies and electron spin resonance (cw-ESR and TR-ESR). The fluorescence of Bodipy units is significantly quenched in the dyads, and the spin-polarized TEMPO signals were observed with TR-ESR, generated by a radical triplet pair mechanism. Efficient EISC (ΦT = 80%) was observed for the dyad with a shorter linker, and the triplet state lifetime of the Bodipy chromophore is exceptionally long (62 μs). The EISC takes 250 ps. Poor ISC was observed for the dyad with a longer linker. The efficient ISC and long-lived triplet excited state in this flexible system are in stark contrast to the previously studied rigid EISC systems. The EISC effect was employed for the first time to perform triplet-triplet annihilation (TTA) upconversion (quantum yield ΦUC = 6.7%).

Photoswitching of triplet-triplet annihilation upconversion with photo-generated radical from hexaphenylbiimidazole

Photoirradiation generated radical from hexaphenyl-biimidazole (HPBI) was used for reversible switching of triplet-triplet annihilation (TTA) upconversion, based on quenching of the photosensitizer triplet state by radical-triplet pair mechanism. Upon 365nm irradiation, the TTA upconversion in a system composed by a boron-dipyrromethene (BODIPY) derivative and perylene, was completely switched off due to quenching of triplet state of photosensitizer by photogenerated radical from HPBI. The upconversion was recovered after leaving the samples in darkness, due to regeneration of HPBI Dimer. The photophysical process involved in the photochromism and photoswitching of TTA upconversion were studied with steady-state UV–vis absorption spectroscopy, nanosecond transient absorption spectroscopy and EPR spectroscopy.