Chiral π-Conjugated Double Helical Aminyl Diradical with the Triplet Ground State.

We report a neutral high-spin diradical of chiral C2-symmetric bis[5]diazahelicene with ΔEST ≈ 0.4 kcal mol-1, as determined by EPR spectroscopy/SQUID magnetometry. The diradical is the most persistent among all high-spin aminyl radicals reported to date by a factor of 20, with a half-life of up to 6 days in 2-MeTHF at room temperature. Its triplet ground state and excellent persistence may be associated with the unique spin density distribution within the dihydrophenazine moiety, which characterizes two effective 3-electron C-N bonds analogous to the N-O bond of a nitroxide radical. The enantiomerically enriched (ee ≥ 94%) (MM)- and (PP)-enantiomers of the precursors to the diradicals are obtained by either preparative chiral supercritical fluid chromatography or resolution via functionalization with the chiral auxiliary of the C2-symmetric racemic tetraamine. The barrier for the racemization of the solid tetraamine is ΔG‡ = 43 ± 0.01 kcal mol-1 in the 483-523 K range. The experimentally estimated lower limit of the barrier for the racemization of a diradical, ΔG‡ ≥ 26 kcal mol-1 in 2-MeTHF at 293 K, is comparable to the DFT-determined barrier of ΔG‡ = 31 kcal mol-1 in the gas phase at 298 K. While the enantiomerically pure tetraamine displays strong chiroptical properties, with anisotropy factor |g| = |Δε|/ε = 0.036 at 376 nm, |g| ≈ 0.005 at 548 nm of the high-spin diradical is comparable to that recently reported triplet ground-state diradical dication. Notably, the radical anion intermediate in the generation of diradical exhibits a large SOMO-HOMO inversion, SHI = 35 kcal mol-1.

Cucurbit[7]uril Enhances Distance Measurements of Spin-Labeled Proteins.

We report complex formation between the chloroacetamide 2,6-diazaadamantane nitroxide radical (ClA-DZD) and cucurbit[7]uril (CB-7), for which the association constant in water, Ka = 1.9 × 106 M-1, is at least 1 order of magnitude higher than the previously studied organic radicals. The radical is highly immobilized by CB-7, as indicated by the increase in the rotational correlation time, τrot, by a factor of 36, relative to that in the buffer solution. The X-ray structure of ClA-DZD@CB-7 shows the encapsulated DZD guest inside the undistorted CB-7 host, with the pendant group protruding outside. Upon addition of CB-7 to T4 Lysozyme (T4L) doubly spin-labeled with the iodoacetamide derivative of DZD, we observe the increase in τrot and electron spin coherence time, Tm, along with the narrowing of interspin distance distributions. Sensitivity of the DEER measurements at 83 K increases by a factor 4-9, compared to the common spin label such as MTSL, which is not affected by CB-7. Interspin distances of 3 nm could be reliably measured in water/glycerol up to temperatures near the glass transition/melting temperature of the matrix at 200 K, thus bringing us closer to the goal of supramolecular recognition-enabled long-distance DEER measurements at near physiological temperatures. The X-ray structure of DZD-T4L 65 at 1.12 Å resolution allows for unambiguous modeling of the DZD label (0.88 occupancy), indicating an undisturbed structure and conformation of the protein.

Cucurbit[7]uril Enhances Distance Measurements of Spin-Labeled Proteins.

We report complex formation between the chloroacetamide 2,6-diazaadamantane nitroxide radical (ClA-DZD) and cucurbit[7]uril (CB-7), for which the association constant in water, Ka = 1.9 × 106 M-1, is at least one order of magnitude higher than the previously studied organic radicals. The radical is highly immobilized by CB-7, as indicated by the increase of the rotational correlation time, τrot, by a factor of 36, relative to that in the buffer solution. The X-ray structure of ClA-DZD@CB-7 shows the encapsulated DZD guest inside the undistorted CB-7 host, with the pendant group protruding outside. Upon addition of CB-7 to T4 Lysozyme (T4L) doubly spin-labeled with the iodoacetamide derivative of DZD, we observe the increase in τrot and electron spin coherence time, Tm, along with the narrowing of inter-spin distance distributions. Sensitivity of the DEER measurements at 83 K increases by a factor 4 - 9, compared to the common spin label such as MTSL, which is not affected by CB-7. Inter-spin distances of 3-nm could be reliably measured in water/glycerol up to temperatures near the glass transition/melting temperature of the matrix at 200 K, thus bringing us closer to the goal of supramolecular recognition-enabled long-distance DEER measurements at near physiological temperatures. The X-ray structure of DZD-T4L 65 at 1.12 Å resolution allows for unambiguous modeling of the DZD label (0.88 occupancy), indicating undisturbed structure and conformation of the protein.

Thermally Ultrarobust S = 1/2 Tetrazolinyl Radicals: Synthesis, Electronic Structure, Magnetism, and Nanoneedle Assemblies on Silicon Surface.

Open-shell organic molecules, including S = 1/2 radicals, may provide enhanced properties for several emerging technologies; however, relatively few synthesized to date possess robust thermal stability and processability. We report the synthesis of S = 1/2 biphenylene-fused tetrazolinyl radicals 1 and 2. Both radicals possess near-perfect planar structures based on their X-ray structures and density-functional theory (DFT) computations. Radical 1 possesses outstanding thermal stability as indicated by the onset of decomposition at 269 °C, based on thermogravimetric analysis (TGA) data. Both radicals possess very low oxidation potentials <0 V (vs. SCE) and their electrochemical energy gaps, Ecell ≈ 0.9 eV, are rather low. Magnetic properties of polycrystalline 1 are characterized by superconducting quantum interference device (SQUID) magnetometry revealing a one-dimensional S = 1/2 antiferromagnetic Heisenberg chain with exchange coupling constant J'/k ≈ -22.0 K. Radical 1 in toluene glass possesses a long electron spin coherence time, Tm ≈ 7 µs in the 40-80 K temperature range, a property advantageous for potential applications as a molecular spin qubit. Radical 1 is evaporated under ultrahigh vacuum (UHV) forming assemblies of intact radicals on a silicon substrate, as confirmed by high-resolution X-ray photoelectron spectroscopy (XPS). Scanning electron microscope (SEM) images indicate that the radical molecules form nanoneedles on the substrate. The nanoneedles are stable for at least 64 hours under air as monitored by using X-ray photoelectron spectroscopy. Electron paramagnetic resonance (EPR) studies of the thicker assemblies, prepared by UHV evaporation, indicate radical decay according to first-order kinetics with a long half-life of 50 ± 4 days at ambient conditions.

Aromatic C-C Bond Cleavage in a Curved π-System of Aminocorannulene.

We report a metal- and oxidant-free aromatic C-C bond cleavage in the curved corannulene skeleton. Reaction of 1-aminocorannulene with hydrazonyl chloride generates an amidrazone intermediate that undergoes facile intramolecular proton migrations and ring annulation to give a 1,2,4-triazole derivative of planar benzo[ghi]fluoranthene, in which the release of strain associated with the curved π-surface and the formation of an aromatic triazole moiety are the driving forces. This report provides new insights into the aromatic C-C bond cleavage.

High-Spin S = 3/2 Ground-State Aminyl Triradicals: Toward High-Spin Oligo-Aza Nanographenes.

We report high-spin aminyl triradicals with near-planar triphenylene backbones. Near-planarity of the fused aminyl radicals and the 2,6,10-triphenylene ferromagnetic coupling unit (FCU), magnetically equivalent to three fused 3,4'-biphenyl FCUs, assures an effective 2pπ-2pπ overlap within the cross-conjugated π-system, leading to an S = 3/2 (quartet) ground state that is well separated from low-spin excited doublet states. Thermal populations of the low-spin (S = 1/2) excited states are detectable both by SQUID magnetometry and electron paramagnetic resonance (EPR) spectroscopy, providing doublet-quartet energy gaps, ΔEDQ, corresponding to >85% population of the quartet ground states at room temperature. Notably, EPR-based determination of ΔEDQ relies on direct detection of the quartet ground state and doublet excited states. The ΔEDQ values are 1.0-1.1 kcal mol-1, with the more sterically shielded triradical having the larger value. The half-life of the more sterically shielded triradical in 2-methyltetrahydrofuran (2-MeTHF) is about 6 h at room temperature. The less sterically shielded triradical in 2-MeTHF decomposes at 158 K with a half-life of about 4 h, while at 195 K, the half-life is still about 2 h. The dominant products of the decay of triradicals are the corresponding triamines, suggesting hydrogen atom abstraction from the solvent as the primary mechanism. This study expands the frontier of the open-shell PAHs/nanographenes, of which the unique electronic, nonlinear optical, and magnetic properties could be useful in the development of novel organic electronics, photonics, and spintronics.

High-Spin (S = 1) Blatter-Based Diradical with Robust Stability and Electrical Conductivity.

Triplet ground-state organic molecules are of interest with respect to several emerging technologies but usually show limited stability, especially as thin films. We report an organic diradical, consisting of two Blatter radicals, that possesses a triplet ground state with a singlet-triplet energy gap, ΔEST ≈ 0.4-0.5 kcal mol-1 (2J/k ≈ 220-275 K). The diradical possesses robust thermal stability, with an onset of decomposition above 264 °C (TGA). In toluene/chloroform, glassy matrix, and fluid solution, an equilibrium between two conformations with ΔEST ≈ 0.4 kcal mol-1 and ΔEST ≈ -0.7 kcal mol-1 is observed, favoring the triplet ground state over the singlet ground-state conformation in the 110-330 K temperature range. The diradical with the triplet ground-state conformation is found exclusively in crystals and in a polystyrene matrix. The crystalline neutral diradical is a good electrical conductor with conductivity comparable to the thoroughly optimized bis(thiazolyl)-related monoradicals. This is surprising because the triplet ground state implies that the underlying π-system is cross-conjugated and thus is not compatible with either good conductance or electron delocalization. The diradical is evaporated under ultra-high vacuum to form thin films, which are stable in air for at least 18 h, as demonstrated by X-ray photoelectron and electron paramagnetic resonance (EPR) spectroscopies.

Bis-Spiro-Oxetane and Bis-Spiro-Tetrahydrofuran Pyrroline Nitroxide Radicals: Synthesis and Electron Spin Relaxation Studies.

Synthesis of bis-spiro-oxetane and bis-spiro-tetrahydrofuran pyrroline nitroxide radicals relies on the Mitsunobu reaction-mediated double cyclizations of N-Boc protected pyrroline tetraols. Structures of the nitroxide radicals are supported by X-ray crystallography. In a trehalose/sucrose matrix at room temperature, the bis-spiro-oxetane nitroxide radical possesses electron spin coherence time, Tm ≈ 0.7 µs. The observed enhanced Tm is most likely associated with strong hydrogen bonding of oxetane moieties to the trehalose/sucrose matrix.

Thiophene-Based Double Helices: Radical Cations with SOMO-HOMO Energy Level Inversion.

We report relatively persistent, open-shell thiophene-based double helices, radical cations 1•+ -TMS12 and 2•+ -TMS8 . Closed-shell neutral double helices, 1-TMS12 and 2-TMS8 , have nearly identical first oxidation potentials, E +/0 ≈ +1.33 V, corresponding to reversible oxidation to their radical cations. The radical cations are generated, using tungsten hexachloride in dichloromethane (DCM) as an oxidant, E +/0 ≈ +1.56 V. EPR spectra consist of a relatively sharp singlet peak with an unusually low g-value of 2.001-2.002, thus suggesting exclusive delocalization of spin density over π-conjugated system consisting of carbon atoms only. DFT computations confirm these findings, as only negligible fraction of spin density is found on sulfur and silicon atoms and the spin density is delocalized over a single tetrathiophene moiety. For radical cation, 1•+ -TMS12 , energy level of the singly occupied molecular orbital (SOMO) lies below the four highest occupied molecular orbitals (HOMOs), thus indicating the SOMO-HOMO inversion (SHI) and therefore, violating the Aufbau principle. 1•+ -TMS12 has a half-life of the order of only 5 min at room temperature. EPR peak intensity of 2•+ -TMS8 , which does not show SHI, is practically unchanged over at least 2 h.

Synthesis and Thin Films of Thermally Robust Quartet (S = 3/2) Ground State Triradical.

High-spin (S = 3/2) organic triradicals may offer enhanced properties with respect to several emerging technologies, but those synthesized to date typically exhibit small doublet quartet energy gaps and/or possess limited thermal stability and processability. We report a quartet ground state triradical 3, synthesized by a Pd(0)-catalyzed radical-radical cross-coupling reaction, which possesses two doublet-quartet energy gaps, ΔEDQ ≈ 0.2-0.3 kcal mol-1 and ΔEDQ2 ≈ 1.2-1.8 kcal mol-1. The triradical has a 70+% population of the quartet ground state at room temperature and good thermal stability with onset of decomposition at >160 °C under an inert atmosphere. Magnetic properties of 3 are characterized by SQUID magnetometry in polystyrene glass and by quantitative EPR spectroscopy. Triradical 3 is evaporated under ultrahigh vacuum to form thin films of intact triradicals on silicon substrate, as confirmed by high-resolution X-ray photoelectron spectroscopy. AFM and SEM images of the ∼1 nm thick films indicate that the triradical molecules form islands on the substrate. The films are stable under ultrahigh vacuum for at least 17 h but show onset of decomposition after 4 h at ambient conditions. The drop-cast films are less prone to degradation in air and have a longer lifetime.

Supramolecular Approach to Electron Paramagnetic Resonance Distance Measurement of Spin-Labeled Proteins.

We demonstrate a host-guest molecular recognition approach to advance double electron-electron resonance (DEER) distance measurements of spin-labeled proteins. We synthesized an iodoacetamide derivative of 2,6-diazaadamantane nitroxide (DZD) spin label that could be doubly incorporated into T4 Lysozyme (T4L) by site-directed spin labeling with efficiency up to 50% per cysteine. The rigidity of the fused ring structure and absence of mobile methyl groups increase the spin echo dephasing time (Tm) at temperatures above 80 K. This enables DEER measurements of distances >4 nm in DZD-labeled T4L in glycerol/water at temperatures up to 150 K with increased sensitivity compared to that of a common spin label such as MTSL. Addition of ß-cyclodextrin reduces the rotational correlation time of the label, slightly increases Tm, and most importantly, narrows (and slightly lengthens) the interspin distance distributions. The distance distributions are in good agreement with simulated distance distributions obtained by rotamer libraries. These results provide a foundation for developing supramolecular recognition to facilitate long-distance DEER measurements at near physiological temperatures.

High-Spin Diradical Dication of Chiral π-Conjugated Double Helical Molecule.

We report an air-stable diradical dication of chiral D2-symmetric conjoined bis[5]diazahelicene with an unprecedented high-spin (triplet) ground state, singlet triplet energy gap, ΔEST = 0.3 kcal mol-1. The diradical dication possesses closed-shell (Kekulé) resonance forms with 16 π-electron perimeters. The diradical dication is monomeric in dibutyl phthalate (DBP) matrix at low temperatures, and it has a half-life of more than 2 weeks at ambient conditions in the presence of excess oxidant. A barrier of ∼35 kcal mol-1 has been experimentally determined for inversion of configuration in the neutral conjoined bis[5]diazahelicene, while the inversion barriers in its radical cation and diradical dication were predicted by the DFT computations to be within a few kcal mol-1 of that in the neutral species. Chiral HPLC resolution provides the chiral D2-symmetric conjoined bis[5]diazahelicene, enriched in (P,P)- or (M,M)-enantiomers. The enantiomerically enriched triplet diradical dication is configurationally stable for 48 h at room temperature, thus providing the lower limit for inversion barrier of configuration of 27 kcal mol-1. The enantiomers of conjoined bis[5]diazahelicene and its diradical dication show strong chirooptical properties that are comparable to [6]helicene or carbon-sulfur [7]helicene, as determined by the anisotropy factors, |g| = |Δε|/ε = 0.007 at 348 nm (neutral) and |g| = 0.005 at 385 nm (diradical dication). DFT computations of the radical cation suggest that SOMO and HOMO energy levels are near-degenerate.

gem-Diethyl Pyrroline Nitroxide Spin Labels: Synthesis, EPR Characterization, Rotamer Libraries and Biocompatibility.

The availability of bioresistant spin labels is crucial for the optimization of site-directed spin labeling protocols for EPR structural studies of biomolecules in a cellular context. As labeling can affect proteins' fold and/or function, having the possibility to choose between different spin labels will increase the probability to produce spin-labeled functional proteins. Here, we report the synthesis and characterization of iodoacetamide- and maleimide-functionalized spin labels based on the gem-diethyl pyrroline structure. The two nitroxide labels are compared to conventional gem-dimethyl analogs by site-directed spin labeling (SDSL) electron paramagnetic resonance (EPR) spectroscopy, using two water soluble proteins: T4 lysozyme and Bid. To foster their use for structural studies, we also present rotamer libraries for these labels, compatible with the MMM software. Finally, we investigate the "true" biocompatibility of the gem-diethyl probes comparing the resistance towards chemical reduction of the NO group in ascorbate solutions and E. coli cytosol at different spin concentrations.

gem-Diethyl Pyrroline Nitroxide Spin Labels: Synthesis, EPR Characterization, Rotamer Libraries and Biocompatibility.

Invited for this month's cover picture is the group of Professor Enrica Bordignon at the Ruhr University Bochum. The cover picture shows an artistic view of E. coli cells and two spin-labeled recombinantly produced proteins, which can be inserted into the cells for EPR studies. The primary sequence of the proteins is schematically shown with the one-letter amino acid code, and cysteine residues are functionalized with the two new gem diethyl nitroxide spin labels designed to better sustain the reducing cellular environment. Read the full text of their Full Paper at 10.1002/open.201900119.

Thermally and Magnetically Robust Triplet Ground State Diradical.

High spin ( S = 1) organic diradicals may offer enhanced properties with respect to several emerging technologies, but typically exhibit low singlet triplet energy gaps and possess limited thermal stability. We report triplet ground state diradical 2 with a large singlet-triplet energy gap, Δ EST ≥ 1.7 kcal mol-1, leading to nearly exclusive population of triplet ground state at room temperature, and good thermal stability with onset of decomposition at ∼160 °C under inert atmosphere. Magnetic properties of 2 and the previously prepared diradical 1 are characterized by SQUID magnetometry of polycrystalline powders, in polystyrene glass, and in other matrices. Polycrystalline diradical 2 forms a novel one-dimensional (1D) spin-1 ( S = 1) chain of organic radicals with intrachain antiferromagnetic coupling of J'/ k = -14 K, which is associated with the N···N and N···O intermolecular contacts. The intrachain antiferromagnetic coupling in 2 is by far strongest among all studied 1D S = 1 chains of organic radicals, which also makes 1D S = 1 chains of 2 most isotropic, and therefore an excellent system for studies of low-dimensional magnetism. In polystyrene glass and in frozen benzene or dibutyl phthalate solution, both 1 and 2 are monomeric. Diradical 2 is thermally robust and is evaporated under ultrahigh vacuum to form thin films of intact diradicals on silicon substrate, as demonstrated by X-ray photoelectron spectroscopy. Based on C-K NEXAFS spectra and AFM images of the ∼1.5 nm thick films, the diradical molecules form islands on the substrate with molecules stacked approximately along the crystallographic a-axis. The films are stable under ultrahigh vacuum for at least 60 h but show signs of decomposition when exposed to ambient conditions for 7 h.

Maximizing NMR signal per unit time by facilitating the e-e-n cross effect DNP rate.

The dynamic nuclear polarization (DNP) efficiency is critically dependent on the properties of the radical, solvent, and solute constituting the sample system. In this study, we focused on the three spin e-e-n cross effect (CE)'s influence on the nuclear longitudinal relaxation time constant T1n, the build-up time constants of nuclear magnetic resonance (NMR) signal, TDNP and DNP-enhancement of NMR signal. The dipolar interaction strength between the electron spins driving the e-e-n process was systematically modulated using mono-, di-, tri-, and dendritic-nitroxide radicals, while maintaining a constant global electron spin concentration of 10 mM. Experimental results showed that an increase in electron spin clustering led to an increased electron spin depolarization, as mapped by electron double resonance (ELDOR), and a dramatically shortened T1n and TDNP time constants under static and magic angle spinning (MAS) conditions. A theoretical analysis reveals that strong e-e interactions, caused by electron spin clustering, increase the CE rate. The three spin e-e-n CE is a hitherto little recognized mechanism for shortening T1n and TDNP in solid-state NMR experiments at cryogenic temperatures, and offers a design principle to enhance the effective CE DNP enhancement per unit time. Fast CE rates will benefit DNP at liquid helium temperatures, or at higher magnetic fields and pulsed DNP, where slow e-e-n polarization transfer rate is a key bottleneck to achieving maximal DNP performance.

S = 1 Tetraazacyclophane Diradical Dication with Robust Stability: A Case of Low-Temperature One-Dimensional Antiferromagnetic Chain.

One-dimensional (1D) spin-1 ( S = 1) chain of organic radicals with low local magnetic anisotropy may provide a better understanding of the low-dimensional magnetism. We report solid-state studies, including single crystal X-ray crystallography, of air-stable tetraazacyclophane diradical dication salt 12·2+·2[Al(OC(CF3)2CH3)4]- with a triplet ground state (Δ EST ≈ 0.5 kcal mol-1). The magnetic behavior for 12·2+ at low temperature is best modeled by 1D spin S = 1 Heisenberg chain with intrachain antiferromagnetic coupling of J'/ k = -5.4 K, which is associated with the interaryl C···C contacts, including π-π interactions. Zero-field splitting value, | D/ hc| ≈ 5.6 × 10-3 cm-1, for 12·2+ is rather small; thus, the 1D chains are characterized by the high degree of isotropicity | D/2 J'| ≈ 7.5 × 10-4. The diradical dication salt possesses extraordinary stability with onset of decomposition at temperature of about 180 °C (∼450 K), based on thermogravimetric analysis and EPR spectroscopy.

Truncated Cross Effect Dynamic Nuclear Polarization: An Overhauser Effect Doppelgänger.

The discovery of a truncated cross-effect (CE) in dynamic nuclear polarization (DNP) NMR that has the features of an Overhauser-effect DNP (OE-DNP) is reported here. The apparent OE-DNP, where minimal µw power achieved optimum enhancement, was observed when doping Trityl-OX063 with a pyrroline nitroxide radical that possesses electron-withdrawing tetracarboxylate substituents (tetracarboxylate-ester-pyrroline or TCP) in vitrified water/glycerol at 6.9 T and at 3.3 to 85 K, in apparent contradiction to expectations. While the observations are fully consistent with OE-DNP, we discover that a truncated cross-effect ( tCE) is the underlying mechanism, owing to TCP's shortened T1e. We take this observation as a guideline and demonstrate that a crossover from CE to tCE can be replicated by simulating the CE of a narrow-line (Trityl-OX063) and a broad-line (TCP) radical pair, with a significantly shortened T1e of the broad-line radical.

Reduction kinetics and electrochemistry of tetracarboxylate nitroxides.

Tetracarboxylate pyrroline nitroxides undergo very fast reduction with ascorbate/glutathione (GSH), with second-order rate constants that are five orders of magnitude greater than those for gem-diethyl pyrroline nitroxides. For tetracarboxylate nitroxides, the electrochemical reduction potentials, measured by square wave voltammetry, are much less negative (by about 0.8 V), compared with the corresponding gem-diethyl nitroxides, while the oxidation potentials become more positive (by about 0.7 V). Electrochemical potentials correlate well via simple regressions with field/inductive parameters such as Swain/Lupton F-parameters (and/or Charton σI-parameters). Rates of reduction with ascorbate/GSH similarly correlate well for four pyrroline nitroxides, except for the slowest reducing gem-diethyl nitroxide. These results suggest that the electron withdrawing groups adjacent to the nitroxide moiety have a strong accelerating impact on the reduction rates, and thus they are not suitable for the design of hydrophilic nitroxides for in vivo applications.

PEGylated, Water-Soluble, Stable Aminyl Radical.

We report the synthesis and kinetic study of PEGylated, water-soluble aminyl radical 2. The radical possesses four mPEG-3 groups replacing four methyl groups in the tert-butyl groups at the 3- and 6-positions of 1,3,6,8-tetra-tert-butyl carbazyl (TTBC). This structure is designed to mitigate the rapid decomposition of the radical via intramolecular 1,5-hydrogen atom transfer (1,5-HAT) that was observed in its constitutional isomer 1-H with four mPEG-3 groups in the vicinity of the nitrogen-centered radical (1- and 8-positions of TTBC). In dry, degassed acetone at 295 K, the radical 2 has a half-life, τ1/2 = 49 h (ΔH‡ = 17.9 ± 0.8 kcal mol-1), which is 3 orders of magnitude longer than that for 1-H, which decays via 1,5-HAT (τ1/2 = 48 s, ΔH‡ = 10.0 ± 0.3 kcal mol-1). Aminyl radical 2 aggregates at ambient conditions in water and has a half-life, τ1/2 = 2 h.