Dimer Radical Cation Research Articles

Dimer radical cation of 4‐thiouracil: a pulse radiolysis and theoretical study

Pulse radiolysis with optical absorption detection has been used to study the reactions of hydroxyl radical (OH•) with 4‐thiouracil (4TU) in aqueous medium. The transient absorption spectrum for the reaction of OH• with 4TU is characterized by λmax 460 nm at pH 7. A second‐order rate constant k(4TU+OH) of 1.7 × 1010 M−1 s−1 is determined via competition kinetics method. The transient is envisaged as a dimer radical cation [4TU]2•+, formed via the reaction of an initially formed radical cation [4TU]•+ with another 4TU. The formation constant of [4TU]2•+ is 1.8 × 104 M−1. The reactions of dibromine radical ion (Br2•−) at pH 7, dichlorine radical ion (Cl2•−) at pH 1, and azide radical (N3•) at pH 7 with 4TU have also produced transient with λmax 460 nm. Density functional theory (DFT) studies at BHandHLYP/6–311 + G(d,p) level in aqueous phase showed that [4TU]2•+ is characterized by a two‐centerthree electron (2c‐3e) [−S∴S−] bond. The interaction energy of [−S∴S−] bond in [4TU]2•+ is −13.01 kcal mol−1. The predicted λmax 457 nm by using the time‐dependent DFT method for [4TU]2•+ is in agreement with experimental λmax. Theoretical calculations also predicted that compared with [4TU]2•+, 4‐thiouridine dimer is more stable, whereas 4‐thiothymine dimer is less stable. Copyright © 2013 John Wiley & Sons, Ltd.

Reaction selectivity in an ionized water dimer: nonadiabatic ab initio dynamics simulations

We study dynamical processes following water dimer ionization. The nonadiabatic dynamical simulations of the water dimer radical cation are performed using a surface hopping technique and a Complete Active Space-Self Consistent Field (CASSCF) method for the description of electronic structure. The main goal of this study is to find out whether a state-dependent reactivity is observed for the water dimer radical cation. We provide a detailed mapping of the potential energy surfaces (PESs) in the relevant coordinates for different electronic states. Dynamical patterns are discussed on the basis of static PES cuts and available experimental data. As a product of the reaction, we observed either proton transferred structure (H3O(+)···OH˙) or various dissociated structures (H3O(+) + OH˙, H2O˙(+) + H2O, H˙ + OH˙ + H2O˙(+)). The relative yields are controlled by the populated electronic state of the radical cation. The proton transfer upon the HOMO electron ionization is an ultrafast process, taking less than 100 fs, in cases of higher energy ionization the dynamical processes occur on longer timescales (200-300 fs). We also discuss the implications of our simulations for the efficiency of the recently identified intermolecular coulomb decay (ICD) process in the water dimer.

Electrochromic devices based on surface-confined Prussian blue or Ruthenium purple and aqueous solution-phase di-n-heptyl viologen

Prototype electrochromic devices (ECDs) based on anodically-colouring thin-film Prussian blue (PB) or Ruthenium purple (RP) and cathodically-colouring aqueous solution-phase di-n-heptyl viologen are described. The initial (‘off’) state of each ECD is set with the PB (or RP) in the colourless reduced form and the di-n-heptyl viologen as the colourless di-cation. Switching the ECDs to the coloured state (‘on’), forms on oxidation the coloured mixed-valence PB (or RP), with simultaneous reduction of the di-n-heptyl viologen di-cation to form the purplish-red di-n-heptyl viologen radical cation dimer salt as a thin film. The overall perceived reversible colour changes were colourless to deep blue/purple for the PB/di-n-heptyl viologen ECDs and colourless to pinkish-purple for the RP/di-n-heptyl viologen ECDs. Using the Commission Internationale de l'Eclairage (CIE) system of colorimetry, the colour stimuli of the ECDs were calculated from in situ visible region spectra recorded under electrochemical control, the depth of colour being controlled by the di-n-heptyl viologen concentration. For the coloured states of the PB/di-n-heptyl viologen ECDs, the CIELAB 1976 colour space coordinates for a D55 illuminant were L⁎=60, a*=22 and b*=−47, and L*=39, a*=47 and b*=−55, respectively for 5 and 10mmoldm−3 di-n-heptyl viologen solution concentrations. For the RP/di-n-heptyl viologen ECDs, the coordinates were L*=70, a*=31 and b*=−27, and L*=63, a*=44 and b*=−34, respectively for 5 and 10mmoldm−3 di-n-heptyl viologen solution concentrations. L* quantifies the lightness, with +a*, −a*, +b* and −b* respectively giving the red, green, yellow and blue directions away from the achromatic point (0, 0).

Hydrogen Bonding in Neutral and Cation Dimers of H2Se with H2O, H2S, and H2Se

Structures, hydrogen bonding, and binding energies of H(4)SeA (A = O, S, Se) dimers and their cation radicals have been studied using DFT-B3LYP, MP2, and CCSD methods with 6-31++G(d,p), cc-pVTZ, and aug-cc-pVTZ basis sets. The binding energy (BE) order of the most stable neutral and cationic dimers have been found to be (H(2)Se···HOH) > (H(2)Se···HSH) > (H(2)Se···HSeH), and (H(2)Se···SeH(2))(+) > (H(2)Se···SH(2))(+) > (HSe···HOH(2))(+), respectively, by B3LYP/6-31++G(d,p) and MP2/aug-cc-pVTZ methods. Higher electronegativity of the heteroatom has been found to result in more stability of the neutral dimer but less of the cationic dimer. Among neutral dimers, structure with more electronegative heteroatom acting as proton donor has been found to be more stable. However, the hemibonded structure has been found to be more stable for the dimer cation radical unless the ionization potentials of the involved heteroatoms are very different, e.g., H(4)SeO(+). Vibrational frequency calculation suggests that an increase in electronegativity of A-atom results in a decrease in Se-H bond strength in H(4)SeA and H(4)SeA(+) dimers. The calculated values of Mulliken atomic charge/spin and hydrogen bond lengths of the dimers and their radical cations have also been discussed.

Tetrathiafulvalene Hetero Radical Cation Dimerization in a Redox-Active [2]Catenane

The electronic properties of tetrathiafulvalene (TTF) can be tuned by attaching electron-donating or electron-withdrawing substituents. An electron-rich macrocyclic polyether containing two TTF units of different constitutions, namely 4,4'-bis(hydroxymethyl)tetrathiafulvalene (OTTFO) and 4,4'-bisthiotetrathiafulvalene (STTFS), has been synthesized. On two-electron oxidation, a hetero radical dimer is formed between OTTFO(•+) and STTFS(•+). The redox behavior of the macrocyclic polyether has been investigated by electrochemical techniques and UV-vis and electron paramagnetic resonance (EPR) spectroscopies. The [2]catenane in which the macrocyclic polyether is mechanically interlocked with the cyclobis(paraquat-p-phenylene) (CBPQT(4+)) ring has also been prepared using template-directed protocols. In the case of the [2]catenane, the formation of the TTF hetero radical dimer is prevented sterically by the CBPQT(4+) ring. After a one-electron oxidation, a 70:30 ratio of OTTFO(•+) to STTFS(•+) is present at equilibrium, and, as a result, two translational isomers of the [2]catenane associated with these electronically different isomeric states transpire. EPR titration spectroscopy and simulations reveal that the radical states of the two constitutionally different TTF units in the [2]catenane still experience long-range electronic intramolecular coupling interactions, despite the presence of the CBPQT(4+) ring, when one or both of them are oxidized to the radical cationic state. These findings in the case of both the free macrocyclic polyether and the [2]catenane have led to a deeper fundamental understanding of the mechanism of radical cation dimer formation between constitutionally different TTF units.

Oxidation Reactions of 2-Thiouracil: A Theoretical and Pulse Radiolysis Study

The reaction of hydroxyl radical ((•)OH) with the nucleic acid base analogue 2-thiouracil (1) has been studied by pulse radiolysis experiments and DFT. The generic intermediate radicals feasible for the (•)OH reactions with 1, namely, one electron oxidation product (1(•+)), (•)OH-adducts (3(•), 4(•), and 5(•)), and H-abstracted radicals (6(•) and 7(•)), were characterized by interpreting their electronic and structural properties along with calculated energetics and UV-vis spectra. Pulse radiolysis experiments showed that the transient formed in the reaction of (•)OH with 1 in water at pH 6.5 has λ(max) at 430 nm. A bimolecular rate constant, k(2) of 9.6 × 10(9) M(-1) s(-1), is determined for this reaction via competition kinetics with 2-propanol. The experiments suggested that the transient species could be a dimer radical cation 2(•+), formed by the reaction of 1 with the radical cation 1(•+). For this reaction, an equilibrium constant of 4.7 × 10(3) M(-1) was determined. The transient formed in the reaction of 1 with pulse radiolytically produced Br(2)(•-) at pH 6.5 as well as Cl(2)(•-) at pH 1 has also produced λ(max) at 430 nm and suggested the formation of 2(•+). The calculated UV-vis spectra of the transient species (1(•+), 3(•), 4(•), 5(•), 6(•), and 7(•)) showed no resemblance to the experimental spectra, while that of 2(•+) (λ(max) = 420 nm) agreed well with the experimental value and thus confirmed the formation of 2(•+). The 420 nm peak was due to σ → σ* electronic excitation centered on a 2-center-3-electron (2c-3e) sulfur-sulfur bond [-S∴S-]. 2(•+) is the first reported example of a dimer radical cation in a pyrimidine heterocyclic system. Further, 5-C and 6-C substituted (substituents are -F, -Cl, -NH(2), -N(CH(3))(2), -OCH(3), -CF(3), -CH(3), -CH(2)CH(3), n-propyl, phenyl, and benzyl) and 5,6-disubstituted 2-thiouracil systems have been characterized by DFT and found that the reaction (1 + 1(•+) → 2(•+)) is exergonic (1.12-13.63 kcal/mol) for many of them.

Surface hopping dynamics using a locally diabatic formalism: Charge transfer in the ethylene dimer cation and excited state dynamics in the 2-pyridone dimer

In this work, the advantages of a locally diabatic propagation of the electronic wave function in surface hopping dynamics proceeding on adiabatic surfaces are presented providing very stable results even in challenging cases of highly peaked nonadiabatic interactions. The method was applied to the simulation of transport phenomena in the stacked ethylene dimer radical cation and the hydrogen bonded 2-pyridone dimer. Systematic tests showed the reliability of the method, in situations where standard methods relying on an adiabatic propagation of the wave function and explicit calculation of the nonadiabatic coupling terms exhibited significant numerical instabilities. Investigations of the ethylene dimer radical cation with an intermolecular distance of 7.0 Å provided a quantitative description of diabatic charge trapping. For the 2-pyidone dimer, a complex dynamics was obtained: a very fast (<10 fs) initial S(2)∕S(1) internal conversion; subsequent excitation energy transfers with a characteristic time of 207 fs; and the occurrence of proton coupled electron transfer (PCET) in 26% of the trajectories. The computed characteristic excitation energy transfer time of 207 fs is in satisfactory agreement with the experimental value of 318 fs derived from the vibronic exciton splittings in a monodeuterated 2-pyridone dimer complex. The importance of nonadiabatic coupling for the PCET related to the electron transfer was demonstrated by the dynamics simulations.

From Monomers to π Stacks, from Nonconductive to Conductive: Syntheses, Characterization, and Crystal Structures of Benzidine Radical Cations

Salts that contain radical cations of benzidine (BZ), 3,3',5,5'-tetramethylbenzidine (TMB), 2,2',6,6'-tetraisopropylbenzidine (TPB), and 4,4'-terphenyldiamine (DATP) have been isolated with weakly coordinating anions [Al(OR(F))(4)](-) (OR(F) = OC(CF(3))(3)) or SbF(6)(-). They were prepared by reaction of the respective silver(I) salts with stoichiometric amounts of benzidine or its alkyl-substituted derivatives in CH(2)Cl(2). The salts were characterized by UV absorption and EPR spectroscopy as well as by their single-crystal X-ray structures. Variable-temperature UV/Vis absorption spectra of BZ(·)(+)[Al(OR(F))(4)](-) and TMB(·)(+)[Al(OR(F))(4)](-) in acetonitrile indicate an equilibrium between monomeric free radical cations and a radical-cation dimer. In contrast, the absorption spectrum of TPB(·)(+)SbF(6)(-) in acetonitrile indicates that the oxidation of TPB only resulted in a monomeric radical cation. Single-crystal X-ray diffraction studies show that in the solid state BZ and its methylation derivative (TMB) form radical-cation π dimers upon oxidation, whereas that modified with isopropyl groups (TPB) becomes a monomeric free radical cation. By increasing the chain length, π stacks of π dimers are obtained for the radical cation of DATP. The single-crystal conductivity measurements show that monomerized or π-dimerized radicals (BZ(·)(+), TMB(·)(+), and TPB(·)(+)) are nonconductive, whereas the π-stacked radical (DATP(·)(+)) is conductive. A conduction mechanism between chains through π stacks is proposed.

Photodissociation of pyrene dimer radical cation during the pulse radiolysis–laser flash photolysis combined method

Photodissociation of pyrene (Py) dimer radical cation (Py2∙+) giving pyrene radical cation (Py∙+) and Py and subsequent regeneration of Py2∙+ by association of Py∙+ and Py were directly observed during the pulse radiolysis–laser flash photolysis combined method at room temperature. When Py2∙+ was excited at the local excitation band with the 532-nm laser flash, the rapid growth and decay of monomeric Py∙+ were observed at 460 nm. The dissociation of Py2∙+ proceeded via a one-photon process to give the ground-state Py∙+(D0) and Py in the quantum yield (Φdiss) of (2.9 ± 0.9) × 10−3. It was shown that Py∙+ decayed with a time constant of several tens of nanoseconds, indicating that the association of Py∙+ with Py regenerating Py2∙+ proceeds at a diffusion-controlled rate. The photodissociation proceeded from the lowest excited state of Py2∙+, even when Py2∙+ was excited to the higher excited state. The difference between the Φdiss value of Py2∙+ and that previously reported for naphthalene dimer radical cation (Np2∙+) is discussed.

ChemInform Abstract: Charge Delocalization in Self‐Assembled Mixed‐Valence Aromatic Cation Radicals

AbstractReview: 63 refs.

Cucurbit[8]uril-stabilized charge transfer complexes with diquat driven by pH: a SERS study

In this work, we have studied the pH-dependence of the formation of DQCB[8] complexes by surface-enhanced Raman scattering (SERS) spectroscopy. The SERS spectra suggest that at acidic pH CB[8] can form a binary complex with the dication DQ(+2) while at higher pH ternary complexes with the radical cation dimer (DQ(+)˙)(2) and the radical cation-dication dimer (DQ(+)˙DQ(+2)) are formed. The pH-enhanced diquat (DQ) dimerization inside the cucurbit[8]uril cavity has not been reported until now. In addition, this study provides very valuable information regarding the use of CB[8] functionalized silver nanoparticles as SERS substrate for sensing applications.

Assessment of density functional approximations for the hemibonded structure of the water dimer radical cation

Due to the severe self-interaction errors associated with some density functional approximations, conventional density functionals often fail to dissociate the hemibonded structure of the water dimer radical cation (H(2)O)(2)(+) into the correct fragments: H(2)O and H(2)O(+). Consequently, the binding energy of the hemibonded structure (H(2)O)(2)(+) is not well-defined. For a comprehensive comparison of different functionals for this system, we propose three criteria: (i) the binding energies, (ii) the relative energies between the conformers of the water dimer radical cation, and (iii) the dissociation curves predicted by different functionals. The long-range corrected (LC) double-hybrid functional, ωB97X-2(LP) [J.-D. Chai and M. Head-Gordon, J. Chem. Phys., 2009, 131, 174105], is shown to perform reasonably well based on these three criteria. Reasons that LC hybrid functionals generally work better than conventional density functionals for hemibonded systems are also explained in this work.

Charge Delocalization in Self-Assembled Mixed-Valence Aromatic Cation Radicals

The spontaneous assembly of aromatic cation radicals (D(+•)) with their neutral counterpart (D) affords dimer cation radicals (D(2)(+•)). The intermolecular dimeric cation radicals are readily characterized by the appearance of an intervalence charge-resonance transition in the NIR region of their electronic spectra and by ESR spectroscopy. The X-ray crystal structure analysis and DFT calculations of a representative dimer cation radical (i.e., the octamethylbiphenylene dimer cation radical) have established that a hole (or single positive charge) is completely delocalized over both aromatic moieties. The energetics and the geometrical considerations for the formation of dimer cation radicals is deliberated with the aid of a series of cyclophane-like bichromophoric donors with drastically varied interplanar angles between the cofacially arranged aryl moieties. X-ray crystallography of a number of mixed-valence cation radicals derived from monochromophoric benzenoid donors established that they generally assemble in 1D stacks in the solid state. However, the use of polychromophoric intervalence cation radicals, where a single charge is effectively delocalized among all of the chromophores, can lead to higher-order assemblies with potential applications in long-range charge transport. As a proof of concept, we show that a single charge in the cation radical of a triptycene derivative is evenly distributed on all three benzenoid rings and this triptycene cation radical forms a 2D electronically coupled assembly, as established by X-ray crystallography.

Targeting π‐Conjugated Multiple Donor–Acceptor Motifs Exemplified by Tetrathiafulvalene‐Linked Quinoxalines and Tetrabenz[bc,ef,hi,uv]ovalenes: Synthesis, Spectroscopic, Electrochemical, and Theoretical Characterization

An efficient synthetic approach to a symmetrically functionalized tetrathiafulvalene (TTF) derivative with two diamine moieties, 2-[5,6-diamino-4,7-bis(4-pentylphenoxy)-1,3-benzodithiol-2-ylidene]-4,7-bis(4-pentylphenoxy)-1,3-benzodithiole-5,6-diamine (2), is reported. The subsequent Schiff-base reactions of 2 afford large π-conjugated multiple donor-acceptor (D-A) arrays, for example, the triad 2-[4,9-bis(4-pentylphenoxy)-1,3-dithiolo[4,5-g]quinoxalin-2-ylidene]-4,9-bis(4-pentylphenoxy)-1,3-dithiolo[4,5-g]quinoxaline (8) and the corresponding tetrabenz[bc,ef,hi,uv]ovalene-fused pentad 1, in good yields and high purity. The novel redox-active nanographene 1 is so far the largest known TTF-functionalized polycyclic aromatic hydrocarbon (PAH) with a well-resolved (1)H NMR spectrum. The electrochemically highly amphoteric pentad 1 and triad 8 exhibit various electronically excited charge-transfer states in different oxidation states, thus leading to intense optical intramolecular charge-transfer (ICT) absorbances over a wide spectral range. The chemical and electrochemical oxidations of 1 result in an unprecedented TTF(⋅+) radical cation dimerization, thereby leading to the formation of [1(⋅+)](2) at room temperature in solution due to the stabilizing effect, which arises from strong π-π interactions. Moreover, ICT fluorescence is observed with large solvent-dependent Stokes shifts and quantum efficiencies of 0.05 for 1 and 0.035 for 8 in dichloromethane.

Structural and dynamic aspects of electron transfer in proteins — highly organized natural nanostructures

The review briefly outlines theoretical models developed in 1990s to describe electron transfer reactions (ETR) in proteins, as well as different variants of improvements in these models proposed by the present authors to describe ETR in reaction centers (RC) of photosynthetic bacteria with consideration of their molecular dynamics in a wide temperature range. Experimental data on electron transfer from reduced proximal heme c-559 of cytochrome to bacteriochlorophyll dimer radical cation P+ in RC from two types of bacteria, viz., native and mutant RC from Rps. viridis and native RC from Rps. sulfoviridis were analyzed within the framework of the models which take into account the quantum and classical (including diffusive) degrees of freedom responsible for reorganization of the protein globule.

Dimer Radical Cations of Indole and Indole-3-carbinol: Localized and Delocalized Radical Cations of Diindolylmethane

Extending our previous study on the title species (J. Phys. Chem. A2010, 114, 6787), we investigated the dimer cations that are formed on oxidation of the glucobrassin derivatives indole-3-carbinol (I3C) and diindolylmethane (DIM) and of parent indole (I). Radiolysis in ionic liquid and Ar matrices shows that, at sufficiently high concentrations and/or on annealing the solid glasses, intense intermolecular charge-resonance (CR) absorption bands in the NIR herald the formation of sandwich-type dimer cations. The molecular and electronic structure of these species is modeled by calculations with the double-hybrid B2-PLYP-D density functional method which yields predictions in good accord with experiment. The radical cation of DIM also shows a CR band, but unlike in the case of I and I3C, its occurrence is not dependent on the concentration but instead on the solvent: in ionic liquid the CR band is initially absent and arises only on annealing, whereas in Ar matrices it is present from the outset and undergoes blue shifting and sharpening on annealing. These puzzling findings are rationalized on the basis of B2-PLYP-D calculations which predict that neutral DIM exists in the form of two conformers, present in different relative amounts in the two experiments, which on vertical ionization form distinct radical cations, a nonsymmetric one where the odd electron is largely localized on one of the two indole moieties and one with C(2) symmetry where charge and spin are completely delocalized over both halves of the molecule, thus giving rise to an intramolecular CR transition. On annealing, the nonsymmetric cation relaxes to a similarly delocalized structure with C(s) symmetry, thus explaining the observed increase and the shift of the CR band. We believe that DIM(•+) represents the first example of a radical cation which can exist under the same conditions as a localized and a delocalized complex cation.

Radiation Induced Redox Reactions and Fragmentation of Constituent Ions in Ionic Liquids. 2. Imidazolium Cations

In part 1 of this study, radiolytic degradation of constituent anions in ionic liquids (ILs) was examined. The present study continues the themes addressed in part 1 and examines the radiation chemistry of 1,3-dialkyl substituted imidazolium cations, which currently comprise the most practically important and versatile class of ionic liquid cations. For comparison, we also examined 1,3-dimethoxy- and 2-methyl-substituted imidazolium and 1-butyl-4-methylpyridinium cations. In addition to identification of radicals using electron paramagnetic resonance spectroscopy (EPR) and selective deuterium substitution, we analyzed stable radiolytic products using (1)H and (13)C nuclear magnetic resonance (NMR) and tandem electrospray ionization mass spectrometry (ESMS). Our EPR studies reveal rich chemistry initiated through "ionization of the ions": oxidation and the formation of radical dications in the aliphatic arms of the parent cations (leading to deprotonation and the formation of alkyl radicals in these arms) and reduction of the parent cation, yielding 2-imidazolyl radicals. The subsequent reactions of these radicals depend on the nature of the IL. If the cation is 2-substituted, the resulting 2-imidazolyl radical is relatively stable. If there is no substitution at C(2), the radical then either is protonated or reacts with the parent cation forming a C(2)-C(2) σσ*-bound dimer radical cation. In addition to these reactions, when methoxy or C(α)-substituted alkyl groups occupy the N(1,3) positions, their elimination is observed. The elimination of methyl groups from N(1,3) was not observed. Product analyses of imidazolium liquids irradiated in the very-high-dose regime (6.7 MGy) reveal several detrimental processes, including volatilization, acidification, and oligomerization. The latter yields a polymer with m/z of 650 ± 300 whose radiolytic yield increases with dose (~0.23 monomer units per 100 eV for 1-methyl-3-butylimidazolium trifluorosulfonate). Gradual generation of this polymer accounts for the steady increase in the viscosity of the ILs upon irradiation. Previous studies at lower dose have missed this species due to its wide mass distribution (stretching out to m/z 1600) and broad NMR lines, which make it harder to detect at lower concentrations. Among other observed changes is the formation of water immiscible fractions in hydrophilic ILs and water miscible fractions in hydrophobic ILs. The latter is due to anion fragmentation. The import of these observations for use of ILs as extraction solvents in nuclear cycle separations is discussed.

Weak Ferromagnetism and Strong Spin−Spin Interaction Mediated by the Mixed-Valence Ethynyltetrathiafulvalene-Type Ligand

A new chromium complex with ethynyltetrathiafulvalene (TTF)-type ligands, [CrCyclam(C≡C-5-methyl-4'5'-ethylenedithio-TTF)(2)]OTf ([1]OTf), was synthesized. The cyclic voltammetry of the complex shows two reversible oxidation waves owing to the first and second oxidation of the TTF unit. The electrochemical oxidation of [1]OTf in a Bu(4)NClO(4) or Bu(4)NBF(4) solution of a 1:1 acetonitrile-chlorobenzene mixture gave isostructural crystals of [1][ClO(4)](2)(PhCl)(2)(MeCN) and [1][BF(4)](2)(PhCl)(2)(MeCN), where two mixed-valence TTF units of adjacent complexes form a dimer radical cation. The crystal structures are characterized by an alternating chain of S = 3/2 Cr(3+)Cyclam units and S = ½ (TTF)(2)(+) dimers. These two paramagnetic components are connected directly by an ethynyl group, resulting in a strong intrachain spin-spin interaction of 2J/k(B) = -30 and -28 K for [ClO(4)](-) and [BF(4)](-) salts, respectively (H = -2J∑(i)S(i)·S(i+1)). Both salts show a weak ferromagnetic transition at 23 K thanks to interchain antiferromagnetic interaction between TTF dimers. The remanent magnetizations and coercive forces of nonoriented samples at 1.8 K are 0.016 μ(B) and 90 mT for the [ClO(4)](-) salt and 0.010 μ(B) and 50 mT Oe for the [BF(4)](-) salt, respectively. The weak ferromagnetism is attributed to the Dzyaloshinsky-Moriya interaction between adjacent TTF dimers and/or the single-ion anisotropy of [1](2+).

Mechanically Stabilized Tetrathiafulvalene Radical Dimers

Two donor-acceptor [3]catenanes-composed of a tetracationic molecular square, cyclobis(paraquat-4,4'-biphenylene), as the π-electron deficient ring and either two tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) containing macrocycles or two TTF-butadiyne-containing macrocycles as the π-electron rich components-have been investigated in order to study their ability to form TTF radical dimers. It has been proven that the mechanically interlocked nature of the [3]catenanes facilitates the formation of the TTF radical dimers under redox control, allowing an investigation to be performed on these intermolecular interactions in a so-called "molecular flask" under ambient conditions in considerable detail. In addition, it has also been shown that the stability of the TTF radical-cation dimers can be tuned by varying the secondary binding motifs in the [3]catenanes. By replacing the DNP station with a butadiyne group, the distribution of the TTF radical-cation dimer can be changed from 60% to 100%. These findings have been established by several techniques including cyclic voltammetry, spectroelectrochemistry and UV-vis-NIR and EPR spectroscopies, as well as with X-ray diffraction analysis which has provided a range of solid-state crystal structures. The experimental data are also supported by high-level DFT calculations. The results contribute significantly to our fundamental understanding of the interactions within the TTF radical dimers.

Greatly Enhanced Intermolecular π-Dimer Formation of a Porphyrin Trimer Radical Trications through Multiple π Bonds

A trefoil-like porphyrin trimer linked by triphenylamine (TPA-TPZn(3)) was synthesized. A three-electron oxidation of TPA-TPZn(3) forms a radical trication (TPA-TPZn(3)(3+)), in which each porphyrin ring undergoes a one-electron oxidation. The radical trication TPA-TPZn(3)(3+) spontaneously dimerizes to afford (TPA-TPZn(3))(2)(6+) in CH(2)Cl(2) . The characteristic charge-resonance band due to the charge delocalization over the π system of (TPA-TPZn(3))(2)(6+) was observed in the NIR region. The initial oxidation potential of TPA-TPZn(3) is negatively shifted relative to that of the corresponding monomer porphyrin, which results from the stabilization of the oxidized state of TPA-TPZn(3) associated with the dimerization. The thermodynamic parameters (i.e., ΔH, ΔS, and ΔG) for the formation of (TPA-TPZn(3))(2)(6+) were determined by measuring Vis/NIR spectra at various temperatures. The formation constant of (TPA-TPZn(3))(2)(6+) is significantly larger than that of the radical cation dimer of the corresponding monomer porphyrin (e.g., over 2000-fold at 233 K). The electronic states were investigated using EPR spectroscopic analysis. The greatly enhanced dimerization of TPA-TPZn(3)(3+) results from multiple π-bond formation between the porphyrin radical cations.