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Organic radicals have long been suggested as candidates for organic magnets and components in organic spintronic devices. Herein, we demonstrate spin current emission from an organic radical film via spin pumping at room temperature. We present the synthesis and the thin film preparation of a Blatter-type radical with outstanding stability and low roughness. These features enable the fabrication of a radical/ferromagnet bilayer, in which the spin current emission from the organic radical layer can be reversibly reduced when the ferromagnetic film is brought into simultaneous resonance with the radical. The results provide an experimental demonstration of a metal-free organic radical layer operating as a spin source, opening a new avenue for the development of purely organic spintronic devices and bridging the gap between potential and real applications.

The Overhauser effect in the dynamic nuclear polarization (DNP) of non-conducting solids has drawn much attention due to the potential for efficient high-field DNP as well as a general interest in the underlying principles that enable the Overhauser effect in small molecules. We recently reported the observation of 1H and 2H Overhauser effects in H3C- or D3C-functionalized Blatter radical analogs, which we presumed to be caused by methyl rotation. In this work, we look at the mechanism for methyl-driven Overhauser DNP in greater detail, considering methyl librations and tunneling in addition to classical rotation. We predict the temperature dependence of these mechanisms using density functional theory and spin dynamics simulations. Comparisons with results from ultralow-temperature magic angle spinning-DNP experiments revealed that cross-relaxation at temperatures above 60 K originates from both libration and rotation, while librations dominate at lower temperatures. Due to the zero-point vibrational nature of these motions, they are not quenched by very low temperatures, and methyl-driven Overhauser DNP is expected to increase in efficiency down to 0 K, predominantly due to increases in nuclear relaxation times., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

3,3',3''-(Benzene-1,3,5-triyl)tris(1-phenyl-1H-benzo[e][1,2,4]triazin-4-yl) (1) is a C 3 -symmetrical triradical comprised of three Blatter radical units connected at the 1, 3, 5 positions of a central trimethylenebenzene core. This triradical has an excellent air, moisture, and thermal stability. Single-crystal XRD indicates that triradical 1 adopts a propeller-like geometry with the benzotriazinyl moieties twisted by 174.1(2)° and packs in 1D chains along the c axis to form an extensive network of weak intermolecular interactions. Frozen solution continuous wave (CW) EPR spectra and variable-temperature field-sweep echo-detected (FSED) spectra revealed an intramolecular ferromagnetic exchange within the spin system, supporting a quartet S = 3/2 ground state. DFT calculations further supported these experimental findings., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Addition of PhLi to 7-(CF 3 )benzo[ e ][1,2,4]triazine at -78 °C gives the "super stable" Blatter radical in high yields, while above -5 °C two additional products are formed. XRD analysis revealed the formation of a "trimer" and a benzo[ f ][1,2,4]triazepine via a novel mechanism. The latter is formed from the anion generated from the isolated radical, which suggests its instability in organic batteries.

The effect of pressure on the α and β polymorphs of a derivative of Blatter's radical, 3-phenyl-1-(pyrid-2-yl)-1,4-dihydrobenzo[ e ][1,2,4]triazin-4-yl, has been investigated using single-crystal X-ray diffraction to maximum pressures of 5.76 and 7.42 GPa, respectively. The most compressible crystallographic direction in both structures lies parallel to π-stacking interactions, which semiempirical Pixel calculations indicate are also the strongest interactions present. The mechanism of compression in perpendicular directions is determined by void distributions. Discontinuities in the vibrational frequencies observed in Raman spectra measured between ambient pressure and ∼5.5 GPa show that both polymorphs undergo phase transitions, the α phase at 0.8 GPa and the β phase at 2.1 GPa. The structural signatures of the transitions, which signal the onset of compression of initially more rigid intermolecular contacts, were identified from the trends in the occupied and unoccupied volumes of the unit cell with pressure and in the case of the β phase by deviations from an ideal model of compression defined by Birch-Murnaghan equations of state., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The Overhauser effect is unique among DNP mechanisms in that it requires the modulation of the electron-nuclear hyperfine interactions. While it dominates DNP in liquids and metals, where unpaired electrons are highly mobile, Overhauser DNP is possible in insulating solids if rapid structural modulations are linked to a modulation in hyperfine coupling. Herein, we report that Overhauser DNP can be triggered by the strategic addition of a methyl group, demonstrated here in a Blatter's radical. The rotation of the methyl group leads to a modulation of the hyperfine coupling to its protons, which in turn facilitates electron-nuclear cross-relaxation. Removal of the methyl protons, through deuteration, quenches the process, as does the reduction of the hyperfine coupling strength. This result suggests the possibility for the design of tailor-made Overhauser DNP polarizing agents for high-field MAS-DNP.

The crystal structure of Blatter's radical (1,3-diphenyl-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl) has been investigated between ambient pressure and 6.07 GPa. The sample remains in a compressed form of the ambient-pressure phase up to 5.34 GPa, the largest direction of strain being parallel to the direction of π-stacking interactions. The bulk modulus is 7.4 (6) GPa, with a pressure derivative equal to 9.33 (11). As pressure increases, the phenyl groups attached to the N1 and C3 positions of the triazinyl moieties of neighbouring pairs of molecules approach each other, causing the former to begin to rotate between 3.42 to 5.34 GPa. The onset of this phenyl rotation may be interpreted as a second-order phase transition which introduces a new mode for accommodating pressure. It is premonitory to a first-order isosymmetric phase transition which occurs on increasing pressure from 5.34 to 5.54 GPa. Although the phase transition is driven by volume minimization, rather than relief of unfavourable contacts, it is accompanied by a sharp jump in the orientation of the rotation angle of the phenyl group. DFT calculations suggest that the adoption of a more planar conformation by the triazinyl moiety at the phase transition can be attributed to relief of intramolecular H...H contacts at the transition. Although no dimerization of the radicals occurs, the π-stacking interactions are compressed by 0.341 (3) Å between ambient pressure and 6.07 GPa.

The crystal structure and solid-state packing of 4-chloro-5 H -1,2,3-dithiazol-5-one and two polymorphs of 4-chloro-5 H -1,2,3-dithiazole-5-thione were analyzed and compared to structural data of similar systems. These five-membered S,N-rich heterocycles are planar with considerable bond localization. All three structures demonstrate tight solid-state packing without voids which is attributed to a rich network of short intermolecular electrostatic contacts. These include S δ+ …N δ- , S δ+ …O δ- , S δ+ …Cl δ- and S δ+ …S δ- interactions that are well within the sum of their van der Waals radii (∑ VDW ). B3LYP, BLYP, M06, mPW1PW, PBE and MP2 were employed to calculate their intramolecular geometrical parameters, the Fukui condensed functions to probe their reactivity, the bond order, Bird Index and NICS(1) to establish their aromaticity.

The pyren-1'-yl-functionalized dithiadiazolyl (DTDA) radical, C 16 H 9 CNSSN (1), is monomeric in solution and exhibits fluorescence in the deep-blue region of the visible spectrum (440 nm) upon excitation at 241 nm. The salt [1][GaCl 4 ] exhibits similar emission, reflecting the largely spectator nature of the radical in the fluorescence process, although the presence of the radical leads to a modest quenching of emission (Φ F = 98% for 1 + and 50% for 1) through enhancement of non-radiative decay processes. Time-dependent density functional theory studies on 1 coupled with the similar emission profiles of both 1 + and 1 are consistent with the initial excitation being of predominantly pyrene π-π* character. Spectroscopic studies indicate stabilization of the excited state in polar media, with the fluorescence lifetime for 1 (τ = 5 ns) indicative of a short-lived excited state. Comparative studies between the energies of the frontier orbitals of pyren-1'-yl nitronyl nitroxide (2, which is not fluorescent) and 1 reveal that the energy mismatch and poor spatial overlap between the DTDA radical SOMO and the pyrene π manifold in 1 efficiently inhibit the non-radiative electron-electron exchange relaxation pathway previously described for 2. Solid-state films of both 1 and [1][GaCl 4 ] exhibit broad emission bands at 509 and 545 nm, respectively. Incorporation of 1 within a host matrix for OLED fabrication revealed electroluminescence, with CIE coordinates of (0.205, 0.280) corresponding to a sky-blue emission. The brightness of the device reached 1934 cd/m 2 at an applied voltage of 16 V. The crystal structure of 1 reveals a distorted π-stacked motif with almost regular distances between the pyrene rings but alternating long-short contacts between DTDA radicals. Solid state measurements on a thin film of 1 reveal emission occurs at shorter wavelengths (375 nm) whereas conductivity measurements on a single crystal of 1 show a photoconducting response at longer wavelength excitation (455 nm).

Reacting N-aryliminophosphoranes with 1-(het)aroyl-2-aryldiazenes in preheated diphenyl ether at ca. 150-250 °C for 5-25 min affords in most cases the 1,3-diaryl-1,4-dihydrobenzo[e][1,2,4]triazin-4-yls (aka Blatter radicals) in moderate to good yields. All new compounds are fully characterized, including EPR and CV studies for the radicals. Single-crystal X-ray structures of 1-benzoyl-2-(perfluorophenyl)diazene and 1-(perfluorophenyl)-3-phenyl-1,4-dihydrobenzo[e][1,2,4]triazinyl are also presented.

Two planarized analogues of the prototypical Blatter radical (1), peri-annulated 1S and 1O , are demonstrated and provide a new platform for molecular and supramolecular engineering, and for tuning electronic and magnetic properties of the radical. Planarization of 1 results in bathochromic shift to the near-IR region, greater spin delocalization, and anodic shift of the reduction potential only for 1S . Magnetization studies revealed nearly ideal paramagnetic behavior at high temperatures for both radicals 1S and 1O with one-dimensional ferromagnetic interaction in the former (2J=14.4 cm(-1) ) and antiferromagnetic interactions in 1O at low temperatures., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

3-Adamantyl-1-phenyl-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl (4) crystallizes as chains of radicals where the spin bearing benzotriazinyl moieties are isolated from each other. Magnetic susceptibility studies in the 5-300 K temperature region indicate that radical 4 demonstrates typical paramagnetic behavior stemming from non-interacting S = ½ spins.

A simple, one-pot method for the preparation of 1-aryl-3-phenyl-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl radicals by addition of aryllithium to the readily available 3-phenylbenzo[e][1,2,4]triazine followed by aerial oxidation is described. The intermediate anion is also trapped as an N-benzyloxycarbonyl derivative and purified prior to deprotection and oxidation to the radical. The method was demonstrated for nine (het)arenes, and the regioselectivity of nucleophilic addition to the benzo[e][1,2,4]triazine and trapping of the intermediate anion with electrophiles was assessed computationally.

Tetraphenylhexaazaanthracene (TPHA), a fluorescent zwitterionic biscyanine with a closed-shell singlet ground state, on treatment with manganese dioxide or phenyliodine bis(trifluoroacetate) (PIFA), undergoes oxidative dimerization to give a near-zero dipole scissor 5,5'-dimer DI-TPHA. Both acene components of the new dimer DI-TPHA maintain their biscyanine closed-shell singlet ground state motifs, as judged by analysis of both single crystal X-ray crystallographic and density functional theory computational studies; however, unlike TPHA, DI-TPHA is only very weakly fluorescent.

Tetraphenylhexaazaanthracene, TPHA-1, is a fluorescent zwitterionic biscyanine with a closed-shell singlet ground state. TPHA-1 overcomes its weak 16π antiaromaticity by partitioning its π system into 6π positive and 10π negative cyanines. The synthesis of TPHA-1 is low yielding and accompanied by two analogous TPHA isomers: the deep red, non-charge-separated, quinoidal TPHA-2, and the deep green TPHA-3 that partitions into two equal but oppositely charged 8π cyanines. The three TPHA isomers are compared.

1-Phenyl-3-trifluoromethyl-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl is the first example of a hydrazyl radical that shows a reversible sharp spin transition fully completed within 5(1) K. The nominally first-order transition takes place at ca. 58(2) K and proceeds via subtle changes of intra- and interstack interactions between two similar structural phases. The low-temperature phase (5-60 K) is diamagnetic and has a singlet ground state (2Jexp = -166.8 cm(-1), gsolid = 2.0042, ρ = 0.2%) stemming from a multicenter two-electron interaction. The high-temperature phase (60-300 K) is paramagnetic as a result of noninteracting S = 1/2 spins arising from weakly bound dimers.

1,3,7,8-Tetraphenyl-4,8-dihydro-1H-imidazolo[4,5g][1,2,4]benzotriazin-4-yl (5), 8-(4-bromophenyl)-1,3,7-triphenyl-4,8-dihydro-1H-imidazolo[4,5g][1,2,4]benzotriazin-4-yl (6), and 8-(4-methoxyphenyl)-1,3,7-triphenyl-4,8-dihydro-1H-imidazolo[4,5g][1,2,4]benzotriazin-4-yl (7) were characterized by using X-ray diffraction crystallography, variable-temperature magnetic susceptibility studies, and DFT calculations. Radicals 5-7 pack in 1 D π stacks made of radical pairs with alternate short and long interplanar distances. The magnetic susceptibility (χ vs. T) of radicals 5 and 6 exhibit broad maxima at (50±2) and (50±4) K, respectively, and are interpreted in terms of an alternating antiferromagnetic Heisenberg linear chain model with average exchange-interaction values of J = -31.3 and -35.4 cm(-1) (gsolid = 2.0030 and 2.0028) and an alternation parameter a = 0.15 and 0.38 for 5 and 6, respectively. However, radical 7 forms 1 D columns of radical pairs with alternating distances; one of the interplanar distances is significantly longer than the other, which decreases the magnetic dimensionality and leads to discrete dimers with a ferromagnetic exchange interaction between the radicals (2J = 23.6 cm(-1) , 2zJ' = -2.8 cm(-1) , gsolid = 2.0028). Magnetic exchange-coupling interactions in 1,2,4-benzotriazinyl radicals are sensitive to the degree of slippage and inter-radical separation, and such subtle changes in structure alter the fine balance between ferro- and antiferromagnetic interactions., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A two-step route to 1,3-disubstituted benzo- and pyrido-fused 1,2,4-triazinyl radicals is presented. The route involves the N'-(2-nitroarylation) of easily prepared N'-(het)arylhydrazides via nucleophilic aromatic substitution of 1-halo-2-nitroarenes, which in most cases gives N'-(het)aryl-N'-[2-nitro(het)aryl]hydrazides in good yields. Mild reduction of the nitro group followed by an acid-mediated cyclodehydration gives the fused triazines, which upon alkali treatment afford the desired radicals. Fifteen examples of radicals are presented bearing a range of substituents at N-1, C-3, and C-7, including the pyrid-2-yl and 8-aza analogues. This route to the N'-(het)aryl-N'-[2-nitro(het)aryl]hydrazides, which works well with benzo- and picolinohydrazides, required a modification for aceto- and trifluoroacetohydrazides that involved a multistep synthesis of asymmetrically 1,1-diaryl-substituted hydrazines.

1,3-Diphenylbenzo[e][1,2,4]triazin-7(1H)-one, the oxidation product of 1,3-diphenyl-1,4-dihydro-1,2,4-benzotriazin-4-yl (Blatter's radical), reacts with N'-arylbenzamidines in PhMe at ca. 100 °C in the presence of N,N-diisopropylethylamine (Hünig's base) (1 equiv.) to give N'-aryl-N-(1,7-dihydro-7-oxo-1,3-diphenylbenzo[e][1,2,4]triazin-6-yl)benzimidamides in 49-95% yield. In neat AcOH heated at ca. 120 °C, N'–aryl-N-(1,7-dihydro-7-oxo-1,3-diphenylbenzo[e][1,2,4]triazin-6-yl)benzimidamides cyclodehydrate to give the novel 8-substituted 1,3,7-triphenyl-4,8-dihydro-1H-imidazo[4,5-g][1,2,4]benzotriazin-4-yls in 13-81% yield. During the optimization of this cyclodehydration an additional oxazole fused benzotriazinyl radical 1,3,7-triphenyl-1,4-dihydro[1,3]oxazolo[4,5-g][1,2,4]benzotriazin-4-yl was isolated as a side product and characterized. The CV and EPR data of the imidazolo- and oxazolo-fused radicals are presented as well as single crystal X-ray structures of 1,3,7-triphenyl-1,4-dihydro-[1,3]oxazolo[4,5-g][1,2,4]benzotriazin-4-yl and 1,3,7,8-tetraphenyl-4,8-dihydro-1H-imidazo[4,5-g][1,2,4]benzotriazin-4-yl.

7-(Fur-2-yl)benzotriazinyl 1 is the first example of a hydrazyl radical dimer with a thermally accessible triplet state. The triplet exciton (|D| = 0.018 cm(-1), |E| = 0.001 cm(-1)) was observed by solid-state VT-EPR spectroscopy between 5 and 140 K. VT crystallography, DFT calculations and magnetic susceptibility studies reveal a strong temperature dependence of the intra-dimer exchange interaction with J/k ~ -254 + 0.0007T(2).

Resonance Raman (RR) spectroscopy is used to investigate the effect of β-cyclodextrin encapsulation on the structural and photophysical properties of poly(4,4'-diphenylenevinylene). We especially focus on the thermal stability of the polymer. We find that within the range of 10-55 °C the uninsulated polymer exhibits decreased Raman intensity in all the vibrational bands with temperature, along with changes in the relative intensity of the C-C inter-ring stretch mode at 1270 cm(-1) with respect to the ring C-H in-plane symmetric bend at 1187 cm(-1), which provides evidence for conformational changes as a function of temperature. No changes are observed in the intensity of the in-phase CH out-of-plane wag of the vinylene group at 968 cm(-1). Therefore, the conformational changes involve mainly dihedral angle modification between the adjacent phenyl rings toward planarization, and little or no change in the planarity of the trans-vinylene group. The decrease of the optical absorption at 55 °C with respect to that at room temperature and the appearance of a new absorption band at lower energies explain the decrease in the RR intensities and the wavelength dependence of the relative intensities of the Raman band. We note that the conformational change into a more planar geometry, which affects a significant portion of the polymer population, is irreversible and consistent with thermally induced aggregation. Such a planarization is unexpected in view of the usually observed thermochromic behavior of conjugated polymers, which leads to an increase of the energy gap for increasing temperature, as the average dihedral angles are increased due to excitation of a larger number of vibrational modes. Interestingly, the higher threading ratio polymers are resistant to any conformational changes within this temperature range, as reflected by their unchanged RR spectra, due to the rotaxane's ability to suppress intermolecular interactions and aggregation. Interestingly, the conformation of the uninsulated polymer at room temperature appears to be the same as that in the threaded analogues, which suggests that the cyclodextrin cavity hosts the polymer without physically interacting with it.

7-(4-Fluorophenyl) and 7-phenyl-substituted 1,3-diphenyl-1,4-dihydro-1,2,4-benzotriazin-4-yl radicals were characterized by X-ray diffraction analysis and variable-temperature magnetic susceptibility studies. The radicals pack in 1D π stacks of equally spaced slipped radicals with interplanar distances of 3.59 and 3.67 Å and longitudinal angles of 40.97 and 43.47°, respectively. Magnetic-susceptibility studies showed that both radicals exhibit antiferromagnetic interactions. Fitting the magnetic data revealed that the behavior is consistent with 1D regular linear antiferromagnetic chain with J=-12.9 cm(-1), zJ'=-0.4 cm(-1), g=2.0069 and J=-11.8 cm(-1), zJ'=-6.5 cm(-1), g=2.0071, respectively. Magnetic-exchange interactions in benzotriazinyl radicals are sensitive to the degree of slippage, and inter-radical separation and subtle changes in structure alter the fine balance between ferro- and antiferromagnetic interactions., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A Blatter radical is oxidized to benzotriazin-7(H)-one which after amination and subsequent acyl- and aroylation gives N-(benzotriazin-6-yl)carboxamides that undergo ring closure with P(2)S(5) to afford the corresponding thiazolo[5',4':4,5]benzo[1,2-e][1,2,4]triazin-4-yls. These highly delocalized radicals are air stable and show good reversible electrochemical behavior.

X-ray studies show that 1,3-diphenyl-7-(thien-2-yl)-1,4-dihydro-1,2,4-benzotriazin-4-yl (6) adopts a distorted, slipped π-stacked structure of centrosymmetric dimers with alternate short and long interplanar distances (3.48 and 3.52 Å). Cyclic voltammograms of 7-(thien-2-yl)benzotriazin-4-yl 6 show two fully reversible waves that correspond to the -1/0 and 0/+1 processes. EPR and DFT studies on radical 6 indicate that the spin density is mainly delocalized over the triazinyl fragment. Magnetic susceptibility measurements show that radical 6 obeys Curie-Weiss behavior in the 5-300 K region with C=0.378 emu K mol(-1) and θ=+4.72 K, which is consistent with ferromagnetic interactions between S=1/2 radicals. Fitting the magnetic susceptibility revealed the behavior is consistent with an alternating ferromagnetic chain (g=2.0071, J(1) =+7.12 cm(-1), J(2) =+1.28 cm(-1))., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Stille and Suzuki-Miyaura reactions of 7-iodo-1,3-diphenyl-1,4-dihydro-1,2,4-benzotriazin-4-yl are presented as rare examples of cross-coupling reactions with stable organic radicals. Both the Stille and Suzuki-Miyaura reactions are in most cases high yielding but the latter are cleaner while the former are faster and are accompanied by 1,3-diphenyl-1,2,4-benzotriazin-7(H)-one as by-product. A range of 7-aryl and 7-heteroaryl-1,2,4-benzotriazinyls have been synthesized and characterized using standard spectroscopic and spectrometric means.

1,3-Diphenyl-7-trifluoromethyl-1,4-dihydro-1,2,4-benzotriazin-4-yl (4), prepared in high yield via the catalytic oxidation of the corresponding amidrazone 5 by using Pd/C (1.6 mol %) and 1,8-diazabicyclo[5.4.0]undec-7-ene (0.1 equiv) in air, is stable in dichloromethane solutions in the presence of MnO(2) and KMnO(4). Furthermore, radical 4 is thermally stable well past its melting point (160-161 °C) with a decomposition onset temperature of 288 °C. X-ray studies show that radical 4 packs in equidistant slipped π-stacks along the a axis. Cyclic voltammetry shows two fully reversible waves, corresponding to the -1/0, 0/+1 processes. EPR studies indicate that the spin density is mainly delocalized on the triazinyl fragment of the heterocycle. Magnetic susceptibility measurements in the 5-300 K region showed that the radical obeys Curie-Weiss behavior down to 10 K (C = 0.376 emu·K·mol(-1) and θ = +1.41 K) consistent with weak ferromagnetic interactions between S = 1/2 radicals. Subsequent fitting of the magnetic data to a 1D ferromagnetic chain model provided an excellent fit (g = 2.00, J/k = +1.49 K) down to 10 K but failed to reproduce the subsequent decrease in χT at lower temperatures, which has been ascribed to the onset of weaker antiferromagnetic interactions between ferromagnetic chains.

The β-sheet structure associated with chlorinated aromatics (d(Cl···Cl)≈ 4.0 Å) has been implemented to drive formation of π-stacked structures of dithiadiazolyl radicals. Both title compounds exhibit an increase in paramagnetism above 150 K but solid-state EPR studies indicate that the origin of the paramagnetism in these two systems is different.

Unrestricted density functional calculations in combination with the broken-symmetry approach and spin-projection methods have been employed to study a series of formally 4n pi antiaromatic linear and angular polyheteroacenes. Calculations show that the linear polyheteroacene molecules have either stable singlet zwitterionic 6-9 or singlet diradical 5 ground states because they sacrifice the aromaticity of the central arene to form two independent cyanines. The corresponding angular compounds 10-14 have robust triplet states, since they cannot create independent cyanines to escape their overall antiaromaticity. An analysis based on the SOMO-SOMO energy splittings, their spatial distributions, and the spin density populations for the triplet states is presented to clarify the factors that determine their ground state multiplicities.