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The nitroxyl radical 1-methyl-2-azaadamantane N-oxyl (Me-AZADO) exhibits magnetic bistability arising from a radical/dimer interconversion. The transition from the rotationally disordered paramagnetic plastic crystal, Me-AZADO, to the ordered diamagnetic crystalline phase, (Me-AZADO)2, has been conclusively demonstrated by crystal structure determination from high-resolution powder diffraction data and by solid-state NMR spectroscopy. The phase change is characterized by a wide thermal hysteresis with high sensitivity to even small applied pressures. The molecular dynamics of the phase transition from the plastic crystal to the conventional crystalline phase has been tracked by solid-state (1H and 13C) NMR and EPR spectroscopies.

Crystals of the heterocyclic radical naphtho-1,3,2-dithiazolyl NDTA display magnetic bistability with a well-defined hysteretic phase transition at Tc↓ = 128(2) K and Tc↑ = 188(2) K. The magnetic signature arises from a radical/dimer interconversion involving one of the two independent π-radicals in the P1 unit cell. Variable temperature X-ray crystallography has established that while all the radicals in HT-NDTA serve as paramagnetic (S = 1/2) centers, half of the radicals in LT-NDTA form closed-shell N–N σ-bonded dimers (S = 0) and half retain their S = 1/2 spin state. The wide window of bistability (60 K) may be attributed to the large structural changes that accompany the phase transition.

Pressure-induced changes in the solid-state structures and transport properties of three oxobenzene-bridged bisdithiazolyl radicals 2 (R = H, F, Ph) over the range 0–15 GPa are described. All three materials experience compression of their π-stacked architecture, be it (i) 1D ABABAB π-stack (R = Ph), (ii) quasi-1D slipped π-stack (R = H), or (iii) 2D brick-wall π-stack (R = F). While R = H undergoes two structural phase transitions, neither of R = F, Ph display any phase change. All three radicals order as spin-canted antiferromagnets, but spin-canted ordering is lost at pressures

Benzoquino-bis-1,2,3-dithiazole 5 is a closed shell, antiaromatic 16π-electron zwitterion with a small HOMO-LUMO gap. Its crystal structure consists of planar ribbon-like molecular arrays packed into offset layers to generate a "brick-wall" motif with strong 2D interlayer electronic interactions. The spread of the valence and conduction bands, coupled with the narrow HOMO-LUMO gap, affords a small band gap semiconductor with σRT = 1 × 10-3 S cm-1 and Eact = 0.14 eV for transport within the brick-wall arrays. Closure of the band gap to form an all-organic molecular metal with σRT > 101 S cm-1 can be achieved by the application of pressure to 8 GPa.

A critical feature of the electronic structure of oxobenzene-bridged bisdithiazolyl radicals 2 is the presence of a low-lying LUMO which, in the solid state, improves charge transport by providing additional degrees of freedom for electron transfer. The magnitude of this multiorbital effect can be fine-tuned by variations in the π-electron releasing/accepting nature of the basal ligand. Here we demonstrate that incorporation of a nitro group significantly stabilizes the LUMO, and hence lowers Ueff, the effective Coulombic barrier to charge transfer. The effect is echoed, at the molecular level, in the observed trend in Ecell, the electrochemical cell potential for 2 with R = F, H and NO2. The crystal structures of the MeCN and EtCN solvates of 2 with R = NO2 have been determined. In the EtCN solvate the radicals are dimerized, but in the MeCN solvate the radicals form superimposed and evenly spaced π-stacked arrays. This highly 1D material displays Pauli-like temperature independent paramagnetic behavior,...

The heterocyclic bisdithiazolyl radical 1b (R1 = Me, R2 = F) crystallizes in two phases. The α-phase, space group P2₁/n, contains two radicals in the asymmetric unit, both of which adopt slipped π-stack structures. The β-phase, space group P2₁/c, consists of cross-braced π-stacked arrays of dimers in which the radicals are linked laterally by hypervalent 4-center 6-electron S···S-S···S σ-bonds. Variable-temperature magnetic susceptibility measurements on α-1b indicate Curie-Weiss behavior (with Θ = -14.9 K), while the dimer phase β-1b is diamagnetic, showing no indication of thermal dissociation below 400 K. High-pressure crystallographic measurements indicate that the cross-braced π-stacked arrays of dimers undergo a wine-rack compression, but the dimer remains intact up to 8 GPa (at ambient temperature). The resistance of β-1b to dissociate under pressure, also observed in its conductivity versus pressure profile, is in marked contrast to the behavior of the related dimer β-1a (R1 = Et, R2 = F), which readily dissociates into a pair of radicals at 0.8 GPa. The different response of the two dimers to pressure has been rationalized in terms of differences in their linear compressibilities occasioned by changes in the degree of cross-bracing of the π-stacks. Dissociation of both dimers can be effected by irradiation with visible (λ = 650 nm) light; the transformation has been monitored by optical spectroscopy, magnetic susceptibility measurements, and single crystal X-ray diffraction. The photoinduced radical pairs persist up to temperatures of 150 K (β-1b) and 242 K (β-1a) before reverting to the dimer state. Variable-temperature optical measurements on β-1b and β-1a have afforded Arrhenius activation energies of 8.3 and 19.6 kcal mol(-1), respectively, for the radical-to-dimer reconversion. DFT and CAS-SCF calculations have been used to probe the ground and excited electronic state structures of the dimer and radical pair. The results support the interpretation that the ground-state interconversion of the dimer and radical forms of β-1a and β-1b is symmetry forbidden, while the photochemical transformation is symmetry allowed.

Irradiation in the solid state of the hypervalent 4c-6e S···S-S···S bridged σ-dimer of a bisdithiazolyl radical leads to its photodissociation into a pair of π-radicals. The transformation has been monitored by optical spectroscopy, single crystal X-ray diffraction, and magnetic susceptibility measurements. As a result of the large electronic reorganization involved in the dimer-to-radical interconversion, the photogenerated S = 1/2 radical state is remarkably thermally stable, persisting to 242 K before reverting to the S = 0 dimer.

Electro-oxidation of the quinoidal bisdithiazole BT in dichloroethane in the presence of [Bu4N][GaBr4] affords the 1:1 radical ion salt [BT][GaBr4], crystals of which belong to the trigonal space group P3. The packing pattern of the radical cations provides a rare example of an organic kagome basket structure, with S = 1/2 radical ion chains located at the triangular corners of a trihexagonal lattice. Magnetic measurements over a wide temperature range from 30 mK to 300 K suggest strongly frustrated AFM interactions on the scale of J/kb ∼ 30 K, but reveal no anomalies that would be associated with magnetic order. These observations are discussed in terms of the symmetry allowed magnetic interactions within and between the frustrated layers.

Semiquinone-bridged bisdithiazolyls 3 represent a new class of resonance-stabilized neutral radical for use in the design of single-component conductive materials. As such, they display electrochemical cell potentials lower than those of related pyridine-bridged bisdithiazolyls, a finding which heralds a reduced on-site Coulomb repulsion U. Crystallographic characterization of the chloro-substituted derivative 3a and its acetonitrile solvate 3a·MeCN, both of which crystallize in the polar orthorhombic space group Pna2(1), revealed the importance of intermolecular oxygen-to-sulfur (CO···SN) interactions in generating rigid, tightly packed radical π-stacks, including the structural motif found for 3a·MeCN in which radicals in neighboring π-stacks are locked into slipped-ribbon-like arrays. This architecture gives rise to strong intra- and interstack overlap and hence a large electronic bandwidth W. Variable-temperature conductivity measurements on 3a and 3a·MeCN indicated high values of σ(300 K) (10(-3) S cm(-1)) with correspondingly low thermal activation energies E(act), reaching 0.11 eV in the case of 3a·MeCN. Overall, the strong performance of these materials as f = ½ conductors is attributed to a combination of low U and large W. Variable-temperature magnetic susceptibility measurements were performed on both 3a and 3a·MeCN. The unsolvated material 3a orders as a spin-canted antiferromagnet at 8 K, with a canting angle φ = 0.14° and a coercive field H(c) = 80 Oe at 2 K.

High-field, single-crystal EPR spectroscopy on a tetragonal bisdiselenazolyl ferromagnet has provided evidence for the presence of easy-axis magnetic anisotropy, with the crystallographic c axis as the easy axis and the ab plane as the hard plane. The observation of a zero-field gap in the resonance frequency is interpreted in terms of an anisotropy field several orders of magnitude larger than that observed in light-heteroatom, nonmetallic ferromagnets and comparable (on a per-site basis) to that observed in hexagonal close packed cobalt. The results indicate that large spin-orbit-induced magnetic anisotropies, typically associated with 3d-orbital-based ferromagnets, can also be found in heavy p-block radicals, suggesting that there may be major opportunities for the development of heavy p-block organic magnetic materials.

Variable pressure and temperature conductivity measurements on the bisthiaselenazolyl radical dimer [1a](2) have established the presence of a weakly metallic state over the pressure range 5-9 GPa. To explore the origin of this metallization we have examined the crystal and molecular structure of [1a](2) as a function of pressure. At ambient pressure the dimer consists of two radicals linked by a hypervalent 4-center 6-electron S...Se-Se...S sigma-bond into an essentially coplanar arrangement. The dimers are packed in cross-braced slipped pi-stack arrays running along the x-direction of the monoclinic (space group P2(1)/c) unit cell. Pressurization to 4 GPa induces little change in the molecular structure of [1a](2) or in the slipped pi-stack crystal architecture. Near 5 GPa, however, stress on the dimer leads to buckling of the two halves of the molecule and a contraction in the metrics of the S...Se-Se...S unit. These structural changes can be understood in terms of an electronic configurational switch from a 4-center 6-electron sigma-bonded dimer to a more conventional pi-bonded arrangement. At the same time the slipped pi-stack arrays undergo a concertina-like compression, and the crystal structure experiences highly anisotropic changes in cell dimensions. DFT calculations on the molecular electronic structure of the dimer indicate a marked decrease in the HOMO-LUMO gap as the dimer buckles. Related solid-state calculations indicate a rapid closure of the valence/conduction band gap in the same pressure region and the formation of a quasi-metallic state. Metallization of [1a](2) thus arises as much from intramolecular changes, which give rise to a collapse of the HOMO-LUMO gap and near coalescence of the valence and conduction bands, as from increased intermolecular interactions, which cause widening and overlap of the band edges.

We report the preparation, crystallization, and solid-state characterization of the first member of a new family of tris(1,9-disubstituted phenalenyl)silicon neutral radicals. In the solid state, the radical packs as weak partial pi-dimers with intermolecular carbon...carbon contacts that fall at the van der Waals atomic separation. Magnetic susceptibility measurements indicate approximately 0.7 Curie spins per molecule from room temperature down to 50 K, below which antiferromagnetic coupling becomes apparent; the compound has a room-temperature single-crystal conductivity of sigmaRT = 2.4 x 10(-6) S cm(-1).

Recent developments in stable radical chemistry have afforded "heavy atom" radicals, neutral open-shell (S = 1/2) molecular species containing heavy p-block elements (S, Se), which display solid-state magnetic properties once considered exclusive to conventional metal-based magnets. These highly spin-delocalized radicals do not associate in the solid state and yet display extensive networks of close intermolecular interactions. Spin density on the heavy atoms allows for increased isotropic and spin-orbit mediated anisotropic exchange effects. Structural variations induced by chemical modification and physical pressure, coupled with ab-initio methods to estimate exchange energies, have facilitated the development of predictive structure/property relationships. These results, coupled with detailed theoretical analyses and magnetic resonance spectroscopic measurements, have provided insight into the magnetic structure of ferromagnetic and spin-canted antiferromagnetic ordered materials as well as an understanding of the importance of spin-orbit coupling contributions to magnetic hysteresis and anisotropy. Isotropic and anisotropic ferromagnetic exchange can also be enhanced indirectly by the incorporation of heavy atoms into nonspin-bearing sites, where they can contribute to multi-orbital spin-orbit coupling.

The alternating ABABAB π-stacked architecture of the EtCN solvate of the iodo-substituted, oxobenzene-bridged bisdithiazolyl radical IBBO (space group Pnma) gives rise to strong ferromagnetic exchange along the π-stacks, and the material orders as a spin-canted antiferromagnet with T(N) = 35 K, with a spontaneous (canted) moment M(spont) = 1.4 × 10(-3) μB and a coercive field H(c) = 1060 Oe (at 2 K). The observation of spin-canting can only be understood in terms of multiorbital contributions to both isotropic and anisotropic exchange interactions, the magnitude of which are enhanced by spin-orbit effects arising from the heavy-atom iodine substituent. Pseudodipolar interactions lead to a net canted moment along the c-axis, while the sublattice magnetization is predicted to possess an easy a-axis.

We report the preparation, crystallization, and solid-state characterization of the first members of a new family of spiro-bis-(1,9-diamino-substituted-phenalenyl)boron neutral radicals. The crystal structures show that the three radicals are monomeric and without close contacts in the crystal lattice. In all cases magnetic susceptibility measurements confirm the presence of free radicals with one unpaired spin per molecule. Two of the new radical compounds are among the most highly conducting neutral organic solids, with room-temperature conductivities reaching sigma(RT) = 4 x 10(-2) S/cm. The measured conductivities correlate with the closest intermolecular contacts in the solid state and with the calculated band dispersions, even though the bandwidths are much smaller than those found in other organic conductors.

The use of neutral π-radicals as building blocks for molecular conductors holds both appeal and challenge. Such systems obviate the need for counterions, as charge transfer is not required to generate charge carriers. Essentially an array of π-radicals should function like atoms in an elemental metal, e.g., sodium, affording a half-filled energy band. Most radicals, however, tend to dimerize, and even when association can be suppressed the resulting low bandwidth W, coupled with a high on-site Coulomb repulsion U, leads to a Mott insulating state. We are pursuing the design and synthesis of stable heterocyclic thiazyl radicals, with a view to generating stable, crystalline materials with a high W/U ratio. The search for these new radicals, the molecular analogues of sodium, is the subject of this presentation.

We report the preparation, crystallization, and solid-state characterization of a benzyl-substituted spirobiphenalenyl radical. The crystal structure shows that the radical is monomeric in the solid state, with the molecules packed in an unusual one-dimensional (1-D) fashion that we refer to as a pi-step stack. This particular mode of 1-D stacking is forced on the lattice arrangement by the presence of the orthogonal phenalenyl units that were specifically incorporated to prevent the crystallization of low-dimensional structures. The structure shows that this strategy is effective, and neighboring molecules in the stack can only interact via the overlap of one pair of active (spin-bearing) carbon atoms per phenalenyl unit, leading to the pi-step structure in which the remaining four active carbon atoms per phenalenyl unit do not interact with nearest neighbor molecules. The magnetic susceptibility data in the temperature range 4-360 K may be fit to an antiferromagnetic Heisenberg S = 1/2 linear chain model with intrachain spin coupling J = -52.3 cm(-1). Despite the uniform stacking, the material has a room temperature conductivity of 1.4 x 10(-3) S/cm and is best described as a Mott insulator.

New synthetic routes to 1,2,3-dithiazolo-1,2,3-dithiazolylium salts, based on double Herz condensations of N-alkylated 2,6-diaminopyridinium salts with sulfur monochloride, have been developed. The two prototypal 1,2,3-dithiazolo-1,2,3-dithiazolyl radicals HBPMe and HBPEt have been prepared and characterized in solution by cyclic voltammetry and EPR spectroscopy. Measured electrochemical cell potentials and computed (B3LYP/6-31G) gas-phase disproportionation enthalpies favor a low on-site Coulombic repulsion energy U in the solid state. The crystal structures of HBPR (R = Me, Et) have been determined by X-ray crystallography (at 293 K). Both consist of slipped pi-stacks of undimerized radicals, with many close intermolecular S- - -S contacts. Magnetic, conductivity, and optical measurements have been performed and the results interpreted in light of extended Hückel band calculations. The crystalline materials are paramagnetic above 100 K, with room-temperature conductivities sigma(RT) of 10(-5)-10(-6) S cm(-1); the slightly greater conductivity of the R = Et compound can be associated with a more well developed band structure. We suggest a Mott-Hubbard insulator ground state for these materials, with an on-site Coulomb repulsion energy U of about 1.0 eV.

Alkylation of the zwitterionic heterocycle 8-chloro-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridine (ClBP) with alkyl triflates affords 8-chloro-4-alkyl-4H-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridin-2-ium triflates [ClBPR][OTf] (R = Me, Et, Pr). Reduction of these salts with decamethylferrocene affords the corresponding ClBPR radicals as thermally stable crystalline solids. The radicals have been characterized in solution by cyclic voltammetry and EPR spectroscopy. Measured electrochemical cell potentials and computed (B3LYP/6-31G) gas-phase disproportionation enthalpies are consistent with a low on-site Coulombic barrier U to charge transfer in the solid state. The crystal structures of ClBPR (R = Me, Et, Pr) have been determined by X-ray crystallography (at 293 K). All three structures consist of slipped pi-stacks of undimerized radicals, with many close intermolecular S.S contacts. ClBPMe undergoes a phase transition at 93 K to a slightly modified slipped pi-stack arrangement, the structure of which has also been established crystallographically (at 25 K). Variable-temperature magnetic and conductivity measurements have been performed, and the results interpreted in light of extended Hückel band calculations. The room-temperature conductivities of ClBPR systems (sigma(RT) approximately 10(-)(5) to 10(-)(6) S cm(-)(1)), as well as the weak 1D ferromagnetism exhibited by ClBPMe, are interpreted in terms of weak intermolecular overlap along the pi-stacks. The latter is caused by slippage of the molecular plates, a feature necessitated by the steric size of the R and Cl groups on the pyridine ring.

The crystal structure and charge transport properties of the prototypal oxobenzene-bridged 1,2,3-bisdithiazolyl radical conductor 3a are strongly dependent on pressure. Compression of the as-crystallized α-phase, space group Fdd2, to 3-4 GPa leads to its conversion into a second or β-phase, in which F-centering is lost. The space group symmetry is lowered to Pbn2₁, and there is concomitant halving of the a and b axes. A third or γ-phase, also space group Pbn2₁, is generated by further compression to 8 GPa. The changes in packing that accompany both phase transitions are associated with an "ironing out" of the ruffled ribbon-like architecture of the α-phase, so that consecutive radicals along the ribbons are rendered more nearly coplanar. In the β-phase the planar ribbons are propagated along the b-glides, while in the γ-phase they follow the n-glides. At ambient pressure 3a is a Mott insulator, displaying high but activated conductivity, with σ(300 K) = 6 × 10(-3) S cm(-1) and E(act) = 0.16 eV. With compression beyond 4 GPa, its conductivity is increased by 3 orders of magnitude, and the thermal activation energy is reduced to zero, heralding the formation of a metallic state. High pressure infrared absorption and reflectivity measurements are consistent with closure of the Mott-Hubbard gap near 4-5 GPa. The results are discussed in the light of DFT calculations on the molecular and band electronic structure of 3a. The presence of a low-lying LUMO in 3a gives rise to high electron affinity which, in turn, creates an electronically much softer radical with a low onsite Coulomb potential U. In addition, considerable crystal orbital (SOMO/LUMO) mixing occurs upon pressurization, so that a metallic state is readily achieved at relatively low applied pressure.

We report the preparation, crystallization, and solid-state characterization of ethyl (3)- and butyl (4)-substituted spiro-biphenalenyl radicals. Both of these compounds are found to be conducting face-to-face pi-dimers in the solid state but with different room-temperature magnetic ground states. At room temperature, 4 exists as a diamagnetic pi-dimer (interplanar separation of approximately 3.1 A), whereas 3 is a paramagnetic pi-dimer (interplanar separation of approximately 3.3 A), and both compounds show phase transitions between the paramagnetic and diamagnetic forms. Electrical resistivity measurements of single crystals of 3 and 4 show that the transition from the high-temperature paramagnetic pi-dimer form to the low-temperature diamagnetic pi-dimer structure is accompanied by an increase in conductivity by about 2 orders of magnitude. This behavior is unprecedented and is very difficult to reconcile with the usual understanding of a Peierls dimerization, which inevitably leads to an insulating ground state. We tentatively assign the enhancement in the conductivity to a decrease in the on-site Coulombic correlation energy (U), as the dimers form a super-molecule with twice the amount of conjugation.

We report the preparation, crystallization, and solid-state characterization of a spiro-biphenalenyl radical. The crystal structure shows that the radical is monomeric in the solid state and withou...

Reductive coupling of 4,5-dichloro-1,2,3-dithiazolylium chloride yields trans-4,4‘-dichloro-1,1‘,2,2‘,3,3‘-tetrathiadiazafulvalene (DC-TAF), the first example of this heterofulvalene system. Ab initio molecular orbital (B3LYP/6-31G**) calculations on prototypal TAF confirm that the closed shell 1Ag state lies 22 kcal mol-1 below the 3Bu diradical triplet. Cyclic voltammetry on DC-TAF reveals two reversible oxidation waves at 0.80 and 1.25 V (in CH3CN, reference SCE). The ESR signal (g = 2.0117) of the radical cation [DC-TAF]+ (in SO2(l)) exhibits a five-line hyperfine coupling pattern with aN = 0.096 mT. DC-TAF forms a series of 1:1 radical ion salts [DC-TAF][X] by electrooxidation in the presence of tetrahedral counterions (X- = BF4-, ClO4-, FSO3-). The crystal structures of these salts are isomorphous, monoclinic space group P21/n, and consist of one-dimensional ladder-like arrays of [DC-TAF]+ radical cations bridged by S- - -S contacts ranging from 3.5 to 3.7 A. Variable-temperature conductivity and ma...

The synthesis and solid-state characterization of the heterocyclic π-radical 1,2,5-thiadiazolo[3,4-b]-1,2,3-dithiazolo[3,4-b]pyrazin-2-yl, 1,2,3-TDTA, is described. The ESR spectrum of 1,2,3-TDTA (in CH2Cl2, 293 K, g = 2.009) confirms a highly delocalized spin distribution, with observable hyperfine coupling to all five nitrogen atoms of the tricyclic molecule (aN = 0.514, 0.343, 0.109, 0.051, and 0.045 mT). While chemical and electrochemical oxidation (E1/2(ox) = 1.14 V vs SCE) of 1,2,3-TDTA requires relatively harsh conditions, reduction is extremely facile (E1/2(red) = 0.15 V vs SCE). More importantly both the observed cell potential Ecell and computed (MNDO) gas-phase enthalpy ΔHdisp for the disproportionation of this and other 1,2,3-dithiazolyls are significantly lower than those observed for their 1,3,2-isomers. Crystals of 1,2,3-TDTA are monoclinic P21/n, with a = 6.6749(16) A, b = 11.7178(14) A, c = 8.6148(14) A, β = 103.297(16)°, and Z = 4. The crystal structure consists of slipped stacks of head...

The presence of two disulfide groups in the tetrathiophenalenyl radical TTPLY leads to a highly delocalized spin distribution and the lowest cell potential ever observed for a monofunctional phenalenyl derivative. While the heteroatom substituents successfully block C-C bond formation, TTPLY nonetheless associates in the solid state to afford the hypervalent S-S-bonded dimer (TTPLY)2.

The condensation of diaminobenzenedithiol with sulfur monochloride leads to the chloride salt of the radical cation of 3,6-dichlorobenzo(1,2-d:4,5-d')bis(1,2,3-dithiazole), dichloro-(BB-123-DTA)(Cl), which can be reduced to neutral dichloro-(BB-123-DTA) with triphenylantimony. A similar condensation with selenium tetrachloride leads, upon reduction, to the corresponding bis(1,2,3-thiaselenazole) dichloro-(BB-123-TSA). The crystal and molecular structures of both compounds have been determined by X-ray diffraction. Both compounds, which are formally antiaromatic 16﷿-systems, exhibit internal bond lengths consistent with a quinoid formulation. The radical cations of both rings have been characterized by ESR spectroscopy; for dichloro-(BB-123-DTA) + g ) 2.0114 and aN ) 0.201 mT, while for dichloro-(BB-123-TSA) + g ) 2.021 and aN ) 0.44 mT. Further oxidation of both rings affords the corresponding dications, both of which have been characterized crystallographically as their AlCl 4 - salts. The structural features of these compounds are consistent with those expected for dithiazolylium (or thiaselenazolylium) derivatives. The structure and redox chemistry of the benzo(1,2-d:4,5-d')bis(1,2,3-dithiazole) framework is discussed in the light of the results of ab initio calculations.

Condensation of oxamidrazone with sulfur dichloride in acetonitrile affords 4,4‘-bis(1,2,3,5-dithiadiazolium) dichloride in moderate yield. Reduction of this salt with triphenylantimony yields the diradical 4,4‘-bis(1,2,3,5-dithiadiazolyl) [S2N2C−CN2S2], which has been isolated and characterized in the solid state as its dimer [S2N2C−CN2S2]2. The diradical is disjoint, and ab initio molecular orbital methods confirm a very small energy gap (

The layered-sheet architecture of the crystal structure of the fluoro-substituted oxobenzene-bridged bisdithiazolyl radical FBBO affords a 2D π-electronic structure with a large calculated bandwidth. The material displays high electrical conductivity for a f = 1/2 system, with σ(300 K) = 2 × 10(-2) S cm(-1). While the conductivity is thermally activated at ambient pressure, with E(act) = 0.10 eV at 300 K, indicative of a Mott insulating state, E(act) is eliminated at 3 GPa, suggesting the formation of a metallic state. The onset of metallization is supported by infrared measurements, which show closure of the Mott-Hubbard gap above 3 GPa.

The bisdithiazolyl radical 1a is dimorphic, existing in two distinct molecular and crystal modifications. The α-phase crystallizes in the tetragonal space group P4̅2(1)m and consists of π-stacked radicals, tightly clustered about 4̅ points and running parallel to c. The β-phase belongs to the monoclinic space group P2(1)/c and, at ambient temperature and pressure, is composed of π-stacked dimers in which the radicals are linked laterally by hypervalent four-center six-electron S···S-S···S σ-bonds. Variable-temperature magnetic susceptibility χ measurements confirm that α-1a behaves as a Curie-Weiss paramagnet; the low-temperature variations in χ can be modeled in terms of a 1D Heisenberg chain of weakly coupled AFM S = (1)/(2) centers. The dimeric phase β-1a is essentially diamagnetic up to 380 K. Above this temperature there is a sharp hysteretic (T↑= 380 K, T↓ = 375 K) increase in χ and χT. Powder X-ray diffraction analysis of β-1a at 393 K has established that the phase transition corresponds to a dimer-to-radical conversion in which the hypervalent S···S-S···S σ-bond is cleaved. Variable-temperature and -pressure conductivity measurements indicate that α-1a behaves as a Mott insulator, but the ambient-temperature conductivity σ(RT) increases from near 10(-7) S cm(-1) at 0.5 GPa to near 10(-4) S cm(-1) at 5 GPa. The value of σ(RT) for β-1a (near 10(-4) S cm(-1) at 0.5 GPa) initially decreases with pressure as the phase change takes place, but beyond 1.5 GPa this trend reverses, and σ(RT) increases in a manner which parallels the behavior of α-1a. These changes in conductivity of β-1a are interpreted in terms of a pressure-induced dimer-to-radical phase change. High-pressure, ambient-temperature powder diffraction analysis of β-1a confirms such a transition between 0.65 and 0.98 GPa and establishes that the structural change involves rupture of the dimer in a manner akin to that observed at high temperature and ambient pressure. The response of the S···S-S···S σ-bond in β-1a to heat and pressure is compared to that of related dimers possessing S···Se-Se···S σ-bonds.

The solid-state characterization of a second or β-phase of the 1,3-phenylene-bridged diselenadiazolyl diradical 1,3-[(Se2N2C)C6H4(CN2Se2)] is reported. Crystals of this β-phase are monoclinic, space group P21/n, with a = 9.108 (6), b = 15.233 (13), c = 16.110 (5) Å, β = 103.37 (5)°, Z = 8. The crystal structure consists of chain-like arrays of discrete dimers (4 per unit cell), although one intradimer Se-Se linkage is notably longer (3.411 Å) than the other three (3.125, 3.196, 3.204 Å). The dimer units lie in chains that are linked by a complex three-dimensional array of Se-Se contacts. Variable-temperature single-crystal conductivity measurements on this phase indicate a band gap of 0.77 eV. Consistent with the conductivity measurements, extended Hückel band structure calculations suggest a relatively isotropic electronic structure.

The synthesis and solid-state characterization of the resonance-stabilized heterocyclic thia/selenazyl radicals 1a-4a is described. While all the radicals crystallize in undimerized slipped pi-stacked arrays, the four crystal structures do not constitute an isomorphous set; crystals of 1a and 3a belong to the orthorhombic space group P2(1)2(1)2(1), while those of 2a and 4a belong to the monoclinic space group P2(1)/n. The origin of the structural dichotomy can be traced back to the packing of the radicals in the P2(1)/n structure, which maximizes intermolecular Se-Se' contacts. There are marked differences in the transport properties of the two groups. Variable temperature conductivity measurements reveal high, but activated, conductivity for the monoclinic pair (2a/4a), with sigma(298 K)10(-3) S cm(-1). The application of physical pressure increases the conductivity of both compounds, with sigma(298 K) at 5 GPa reaching 0.5 S cm(-1) for 2a and 2 S cm(-1) for 4a. Variable-temperature magnetic susceptibility measurements indicate strong antiferromagnetic (AFM) coupling for the monoclinic pair 2a and 4a, the behavior of which has been modeled in terms of a molecular-field modified 1D Heisenberg chain of AFM coupled S = 1/2 centers. Extended Huckel theory band structure calculations and density functional theory first principles methods have been used to develop a qualitative understanding of the conductive and magnetic properties of radicals of the type 1-4 as a function of the degree and direction of slippage of the radical pi-stacks.

The preparation and solid-state characterization of the 1,3-phenylene-bridged bis(dithiadiazolyl) and bis(diselenadiazolyl) diradicals 1,3-[(E2N2C)C6H4(CN2E2)] (E = S, Se) are reported. The isomorphous crystals of 1,3-[(E2N2C)C6H4(CN2E2)] so obtained are tetragonal, space group I41/a. Stacks of diradical molecules, linked vertically in a zigzag fashion through alternaie ends by long E- - -E contacts (mean 3.140/3.284 Å, for E = S/Se), are arranged in pinwheellike clusters about the 41 and ¯4 axes, producing complex patterns of interstack E- - -E contacts. Both compounds show the presence of spin defects in the lattice, and there is a very large enhancement in the paramagnetism of the sulfur compound at high temperatures. The selenium compound is a semiconductor, with a room temperature conductivity of 2 × 10-4 S cm-1. Solid-state NMR experiments find enhanced relaxation times, which have their origin in the presence of a mobile paramagnetic defect. Extended Hückel band structure calculations show the materials to be semiconductors, with band gaps of about 1.0/0.8 eV for E = S/Se. Although the compounds adopt a columnar structure, the calculations indicate significant interactions between the stacks and the materials exhibit well-developed three dimensionality. The enhanced paramagnetism in the sulfur compound is attributed to the presence of thermally generated phase kinks in the lattice, whereas the selenium compound is classified as an intrinsic semiconductor.

A series of five isostructural bisthiaselenazolyl radicals 2 have been prepared and characterized by X-ray crystallography. The crystal structures, all belonging to the tetragonal space group P42(1)m, consist of slipped pi-stack arrays of undimerized radicals packed about 4 centers running along the z-direction, an arrangement which gives rise to a complex lattice-wide network of close intermolecular Se---Se' contacts. Variations in R1 (Et, Pr, CH2CF3) with R2 = Cl lead to significant changes in the degree of slippage of the pi-stacks and hence the proximity of the Se---Se' interactions. By contrast, variations in R2 (Cl, Br, Me) with R1 = Et induce very little change in either the degree of slippage or the intermolecular contacts. Variable-temperature conductivity (sigma) measurements show relatively constant values for the conductivity sigma(300 K) (10(-5)-10(-4) S cm(-1)) and thermal activation energy E(act) (0.27-0.31 eV). Variable-temperature magnetic susceptibility measurements indicate that radicals 2b and 2c (R1 = Pr, CH2CF3; R2 = Cl) behave as weakly antiferromagnetically coupled Curie-Weiss paramagnets, but in 2a, 2d and 2e (R1 = Et; R2 = Cl, Me, Br) ferromagnetic ordering is observed, with T(c) values of 12.8 (R2 = Cl), 13.6 (R2 = Me), and 14.1 K (R2 = Br). The origin of the dramatically different magnetic behavior across the series has been explored in terms of a direct through-space mechanism by means of DFT calculations on individual pairwise exchange energies. These indicate that antiferromagnetic exchange between radicals along the pi-stacks increases with pi-stack slippage.

Synthetic methods have been developed to generate the complete series of resonance-stabilized heterocyclic thia/selenazyl radicals 1a-4a. X-ray crystallographic studies confirm that all four radicals are isostructural, belonging to the tetragonal space group P42(1)m. The crystal structures consist of slipped pi-stack arrays of undimerized radicals packed about 4 centers running along the z direction, an arrangement which gives rise to a complex lattice-wide network of close intermolecular E2---E2' contacts. Variable temperature conductivity (sigma) measurements reveal an increase in conductivity with increasing selenium content, particularly so when selenium occupies the E2 position, with sigma(300 K) reaching a maximum (for E1 = E2 = Se) of 3.0 x 10(-4) S cm(-1). Thermal activation energies E(act) follow a similar profile, decreasing with increasing selenium content along the series 1a (0.43 eV), 3a (0.31 eV), 2a (0.27 eV), 4a (0.19 eV). Variable temperature magnetic susceptibility measurements indicate that all four radicals exhibit S = 1/2 Curie-Weiss behavior over the temperature range 20-300 K. At lower temperatures, the three selenium-based radicals display magnetic ordering. Radical 3a, with selenium positioned at the E1 site, undergoes a phase transition at 14 K to a weakly spin-canted (phi = 0.010 degrees) antiferromagnetic state. By contrast, radicals 2a and 4a, which both possess selenium in the E2 position, order ferromagnetically, with Curie temperatures of T(c) = 12.8 and 17.0 K, respectively. The coercive fields H(c) at 2 K of 2a (250 Oe) and 4a (1370 Oe) are much larger than those seen in conventional light atom organic ferromagnets. The transport properties of the entire series 1a-4a are discussed in the light of Extended Hückel Theory band structure calculations.

A general synthetic route to the resonance-stabilized pyrazine-bridged bisdithiazolyl framework, involving the reductive deprotection of 2,6-diaminopyrazine-bisthiocyanate and cyclization with thionyl chloride, has been developed. An N-methyl bisdithiazolyl radical, 4-methyl-4H-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyrazin-3-yl, has been prepared and characterized in solution by electron paramagnetic resonance spectroscopy and cyclic voltammetry. Its crystal structure has been determined at several temperatures. At 295 K, the structure belongs to the space group Cmca and consists of evenly spaced radicals pi-stacked in an alternating ABABAB fashion along the x-direction. At 123 K, the space group symmetry is lowered by loss of C-centering to Pccn, so that the radicals are no longer evenly spaced along the pi-stack. At 88 K, a further lowering of space group symmetry to P21/c is observed. Extended Hückel Theory band structure calculations indicate a progressive opening of a band gap at the Fermi level in the low-temperature structures. Magnetic susceptibility measurements over the range 4-300 K reveal essentially diamagnetic behavior below 120 K. Variable-temperature single-crystal conductivity (sigma) measurements indicate that the conductivity is activated, even at room temperature, with a room-temperature value sigma RT=0.001 S cm-1 and a thermal activation energy Eact=0.19 eV. Under an applied pressure of 5 GPa, sigma RT is increased by 3 orders of magnitude, but the conductivity remains activated, with Eact being lowered to 0.11 eV at 5.5 GPa.

We report the preparation, crystallization, and solid-state characterization of cycloheptyl and cyclooctyl-substituted spirobiphenalenyl radicals and the corresponding sigma-dimer of the cyclooctyl derivative. The crystal structure shows that the cycloheptyl radical (9) is monomeric in the solid state, with the molecules packed in an unusual one-dimensional (1-D) fashion that we refer to as a pi-chain structure, whereas the cyclooctyl variant exists both as pi-dimer 10 and sigma-dimer 10d. The neutral radical 9 shows the temperature-independent Pauli paramagnetism characteristic of a metal with a magnetic susceptibility, chip approximately 4.5x10(-4) emu/mol and is assigned a resonating valence bond (RVB) ground state. We highlight the relationship between the magnetic properties of the Heisenberg antiferromagnet and the RVB ground state in 1-D and further elucidate the electronic structure of this new class of compounds. Magnetic susceptibility measurements show that 10 is a diamagnetic pi-dimer, whereas 10d is a diamagnetic sigma-dimer. Extended Hückel calculations for 9 indicate that the solid is a one-dimensional organic metal with a bandwidth of about 0.4 eV. Pressed pellet conductivity measurements indicate values of sigmaRT=1.5x10(-3) S/cm for compound 9 and sigmaRT=1.0x10(-6) S/cm for compound 10. The structural results and transport properties are discussed in the light of extended Hückel theory band structure calculations and DFT investigations of the electronic structure of related compounds.

An efficient and versatile synthetic route to resonance stabilized bisselenathiazolyl and bisdiselenazolyl radicals 3 and 4 is described. Structural analysis of 3 and 4 confirm that lattice and pi-delocalization energies are sufficient to offset solid-state dimerization of the radicals and that the two selenium-containing radicals are isostructural with the all-sulfur based system 1. Variable temperature conductivity measurements indicate that sequential replacement of sulfur by selenium leads to a progressive increase in conductivity and reduction in thermal activation energy.

We report the preparation, crystallization, and solid-state characterization of the first two members of a new family of spiro-bis(1,9-disubstituted phenalenyl)boron neutral radicals based solely on oxygen functionalization, and we show that this strategy significantly lowers the electrochemical disproportionation potentials (DeltaE), in comparison with other spiro-bis(1,9-disubstituted phenalenyl)boron salts. In the solid state, these radicals pack in a continuous array of pi-pi-stacked phenalenyl units with very short intermolecular carbon...carbon contacts. These two radicals are among the most highly conducting neutral organic solids, with room temperature conductivities reaching 0.3 S/cm. Magnetic susceptibility measurements show that the radicals do not exist as isolated free radicals, and there is significant spin-spin interaction between the molecules in the solid state as expected from the crystal structures and the calculated band structures; the solid-state properties are best rationalized in terms of the resonating valence bond model.

Polymorphism-the phenomenon that a given compound forms more than one crystalline arrangement of the molecules in the solid state- plays a crucial role in understanding organic conductors, superconductors, and magnets. We have found that solutions of a new phenalenyl radical can give rise to two (nonpolymorphic) crystalline forms depending on whether the crystallization is allowed to proceed in the presence or absence of light. In both cases the crystals take the form of black shining blades and are indistinguishable by optical microscopy. We have fully characterized these crystalline forms, and we show that they differ by the presence or absence of a C-C sigma-bond between the unpaired electrons of the parent radical. These molecular forms crystallize from the same solvent to give rise to a sigma-dimerized insulator and a monomeric radical semiconductor as dictated by the presence or absence of light.

New synthetic methods for heterocyclic 1,3,2-dithiazolyl (DTA) radicals have been developed, and trends in the molecular spin distributions and electrochemical properties of a series of DTA radicals are reported. The crystal structures of [1,2,5]thiadiazolo[3,4-f][1,3,2]benzodithiazol-2-yl (TBDTA) and [1,3,2]pyrazinodithiazol-2-yl (PDTA) have been determined. The structure of TBDTA (at 293 and 95 K) contains two molecules in the asymmetric unit, each of which generates pi-stacked arrays, one consisting of antiparallel chains of centrosymmetrically associated dimers, the other comprising parallel chains of unassociated radicals. The structure of PDTA (at 293 and 95 K) is simpler, consisting of slipped stacks of pi-dimers. Variable-temperature magnetic susceptibility (chi(P)) measurements on TBDTA indicate essentially paramagnetic behavior for the unassociated radical pi-stacks over the range 5-400 K. By contrast PDTA is diamagnetic at all temperatures below 300 K, but between 300 and 350 K the value of chi(P) follows a sharp and well-defined hysteresis loop, with T(C) downward arrow = 297 K and T(C) upward arrow = 343 K. These features are symptomatic of a regime of bistability involving the observed low temperature pi-dimer structure and a putative high-temperature radical pi-stack. A mechanism for the interconversion of the two phases of PDTA and related structures is proposed in which hysteretic behavior arises from cooperative effects associated with the breaking and making of a lattice-wide network of intermolecular S- - -N' and/or S- - -S' interactions.

Application of physical pressure to a ferromagnetic bisdiselenazolyl radical leads to a decrease in pi-stack slippage. Initially, this leads to an increase in the ferromagnetic ordering temperature T(C), which reaches a maximum of 21 K near 1 GPa. At higher pressures, as the pi-stacks become more nearly superimposed, the value of T(C) diminishes.

Ferromagnetic ordering, with a Tc of 12.3 K and a coercive field Hc of 590 Oe (at 2 K), in a π-stacked bisthiaselenazolyl radical conductor with σ(300 K) = 1 × 10-4 S cm-1, demonstrates that both conductive and ferromagnetic properties can be incorporated into a single component molecular material.

The molecular radical 1,3,2-dithiazolo[4,5-b]pyrazin-2-yl (PDTA) exhibits magnetic bistability just above room temperature, undergoing a well-defined hysteretic phase change with TC downward arrow = 297(1) K and TC upward arrow = 343(1) K. The crystal structures of the two phases of PDTA have been determined by single-crystal X-ray diffraction at 323(2) K. LT-PDTA consists of diamagnetic (S = 0) nearly superimposed pi-dimer stacks, while that of HT-PDTA comprises slipped stacks of pi-radicals (S = 1/2). The structural interconversion is suggested to proceed via the cooperative breaking and making of intermolecular S- - -N interactions and an inversion symmetry-preserving "domino cascade" of the pi-stacked rings.

Sublimation of 1,2,3,5-dithiadiazolyl in vacuo affords a triclinic phase of the dimer [HCN2S2]2. The crystals belong to the space group P¯1, a = 6.816(3), b = 13.940(2), c = 14.403(3) Å, α = 116.830(14), β = 98.64(3), γ = 99.18(3)°, FW = 212.4 (for [HCN2S2]2·[N2]0.08) Z = 6. The crystal structure consists of stacked dimers, with three dimers per asymmetric unit. Pairs of asymmetric units, related by an inversion center, generate a pinwheel motif consisting of six dimers. The columnar structure associated with these pinwheels forms close-packed sets of “molecular tubes”. Cosublimation of the radical in the presence of iodine in the mole ratio (HCN2S2:I = 5:1) yields an iodine-doped hexagonal phase of composition [HCN2S2]6[I]1.1. Crystals of this material belong to the space group P61, a = b = 14.132(16), c = 3.352(5) Å, FW = 128.20, Z = 6. The crystal structure consists of sixfold pinwheels in which the now evenly spaced HCN2S2 rings form a spiral about the 61 axis. The iodine atoms lie within the columnar cavity of the pinwheels in a disordered array wrapped tightly about the sixfold screw axis. The single-crystal conductivity of the doped material is 15 S cm-1 at room temperature. Raman spectroscopic and magnetic susceptibility measurements on the doped material are reported.

The preparation and solid-state characterization of the trifunctional radical 1,3,5-benzenetris(1,2,3,5-dithiadiazolyl) [4,4’,4”-(1,3,5-benzenetriyl)tris[1,2,3,5-dithiadiazolyl], 1,3,5-C6H3(CN2S2)3] are described. The crystals belong to the monoclinic space group P21/c, with a = 6.927 (2), b = 19.798 (3), c = 19.393 (3), and β = 99.80 (2) A3. The crystal structure consists of stacks of triradicals running parallel to x. Each radical center associates with a neighboring radical, generating alternating long (mean 3.832 A) and short (mean 3.117 A) interradical S···S contacts along the stack; only two of the three crystallographically distinct bond alternation waves so generated are in-phase. The packing of triradical stacks produces an extensive network of close interstack S···S contacts. The compound is diamagnetic at room temperature, but paramagnetic defects begin to appear near 450 K. The room-temperature single-crystal conductivity is near 10-7 S cm-1. Extended Huckel band structure calculations reveal a band gap of 0.8 eV.

The reaction of oxamidrazone with SCl2 affords 4,4′-bis(1,2,3,5-dithiadiazolium) dichloride, which can be reduced to the corresponding bis(1,2,3,5-dithiadiazolyl) diradical; the electronic structure of the diradical is discussed, and the solid state structure, charge transfer chemistry and transport properties of the dimer [S2N2CCN2S2]2 are described.

The p-type doping of neutral polyfunctional π-radicals with iodine has revealed interesting electronic and structural features. Alternative preparative routes such as electrocrystallization have allowed the isolation of compounds not normally obtainable via sublimation methods.