Charge transfer complexes and cation radical salts of azino-diselenadiazafulvalene

The synthesis and the redox behaviour of electroactive donor molecules incorporating an azino spacer group between a benzoselenazole core and another heterocyclic moiety, either a benzoselenazole one or a thiazole one, are reported. Neutral complexes were obtained with TCNQ and, for the first time with dithiadiazafulvalene or diselenadiazafulvalene derivatives, cation radical salts by electrocrystallization. Crystal structures data of these complexes are presented and their geometries compared with those deduced from theoretical calculations.     

Synthesis of annulated dioxins as electron-rich donors for cation radical salts

The synthesis of a series of new alkoxylated linearly annulated dioxins is described together with their cyclic voltammetric behavior and some preliminary result on their ability to form cation radical salts. Of these dioxins, seven (8, 12, 19, 21, 27, 33, 34) are the first representatives of entirely new heterocyclic systems. Dioxins 8, 21, 22 and 27 gave good quality cation radical salts upon electrocrystallization.     

Electron spin relaxation of new organic conductors: fluroranthenyl radical cation salts

Crystals of conducting fluoranthenyl (FA) radical cation salts (FA₂)⁺X^? with X^? = PF^?₆, AsF^?₆ show ESR linewidths (ΔH_pp) of ≈15 mOe at T = 293 K at microwave(9.5 GHz) and radio frequencies (230-60 MHz). ΔH_pp is independent of orientation. We analysed longitudinal and transverse relaxation and their dependence on temperature. These salts are suitable as magnetic field probes.     

A stable radical-substituted radical cation with strongly ferromagnetic interaction: nitronyl nitroxide-substituted 5,10-diphenyl-5,10-dihydrophenazine radical cation

A stable radical-substituted radical ion with strongly ferromagnetic intramolecular interaction (J) between the radical and radical ion sites is an attractive spin building block of organic magnets. We prepared 2-nitronyl nitroxide-substituted 5,10-diphenyl-5,10-dihydrophenazine radical cation, 1+. The 1+ salt was stable under aerated conditions at room temperature and had a large J/kB value (>/=+700 K).     

Electron molecular vibration coupling in vibrational spectra of BEDT-TTF based radical cation salts

The i.r. and Raman spectra of monovalent bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) based charge transfer salts were investigated. The assignment of the fundamental vibrations of the BEDT-TTF radical cation, the identification of the frequency shifts following the ionization of the molecule, and an interpretation of the vibronic bands revealed in the i.r. spectra of these compounds are reported. A normal coordinate analysis together with a semiempirical MNDO calculation of the radical cation electronic structure were used to obtain the electron-molecular vibration coupling constants. The calculated values are in good agreement with the experimental data.     

Mono- and bisadducts from the addition of thianthrene cation radical salts to cycloalkenes and alkenes

Thianthrene cation radical salts, Th(*)(+) X(-)(X(-) = a, ClO(4)(-); b, PF(6)(-); c, SbF(6)(-)), add to cycloalkenes (C(5)-C(8)) in acetonitrile (MeCN) to form 1,2-bis(5-thianthreniumyl)cycloalkane salts and 1,2-(5,10-thianthreniumdiyl)cycloalkane salts, most of which have now been isolated and characterized. These are called bis- (3, 6, 9, 12) and monoadducts (4, 7, 10, 13). The proportional amount of the monoadduct obtained in the initial stage of the reaction varied with the cycloalkene in the order C(6) < C(5) < C(7) < C(8). Thus, the ratio bis:mono for C(5) and C(7) was, respectively, about 80/20 and 50/50. In contrast, only about 5% of the C(6) monoadduct (7a) and none of 7b,c was obtained, while for C(8) none of the bisadducts 12a-c was found. Bisadducts 3 and 9 lost thianthrene (Th) slowly in MeCN solution and changed into monoadducts 4 and 10. A comparable change from 6a into 7a was not observed. The monoadducts, themselves, lost a proton slowly in dry MeCN and opened into 1-(5-thianthreniumyl)cycloalkenes (5, 8, 11, 14). With 3 and 9, particularly, it was possible to follow with NMR spectroscopy the succession of changes, for example, 3 to 4 to 5. The opening of a monoadduct was made faster by adding a small amount of water to the solution. The bisadducts of 4-methylcyclohexene (15a) and 1,5-cyclooctadiene (17a) were isolated and characterized. Although a small amount of monodduct (16a) of 4-methylcyclohexene was found with NMR spectroscopy, it could not be isolated. Bis- and monoadducts were obtained also in additions of Th(*)(+) ClO(4)(-) to acyclic alkenes, in relative amounts that, again, varied with the alkene. From cis-2-butene the dominant product was the bisadduct (18), while the monoaduct (19) was characterized with NMR spectroscopy but could not be isolated. In contrast, trans-3-hexene gave mainly the monoadduct (21), while the bis adduct (20) could not be isolated. With 4-methyl-cis-2-pentene, both bis- (22) and monoadduct (23) were isolated, the former being dominant. The conversion of 18 into 19 was characterized with NMR spectroscopy. In all cycloalkene bisadducts, the configurational relationship of the two thianthrenium groups was trans, while in the monoadducts, the bonds to the single thianthrene dication were (necessarily) cis. In both bis- and monoadducts of acyclic alkenes, the configuration of the alkene was retained. The mechanisms of addition with retention of configuration, of conversion of a bis- into a monoadduct, and of opening of a monoadduct are discussed. Products were identified with a combination of NMR spectroscopy, X-ray crystallography, elemental analysis, and (for cycloalkene adducts) reaction with thiophenoxide ion.     

Study of the fluorescence of perylene cation radical salts with a near field optical setup

A perylene-acetonitrile solution with TBAP (tetra-n-butylammonium perchlorate) electrocrystallizes on the electrode surface, under opportune conditions. It forms particular needle-like micro-crystals that have been studied recently for their peculiar electrical and optical properties and for the fundamental processes involved in the electron transfer responsible for the electrocrystallization. These intriguing structures present various fractal-like morphological organizations and diverse crystal shapes on the same deposition process. Up to now these formations have been studied optically by conventional standard microscopy. We introduce here a novel methodology to collect information on the actual orientation and crystal structure by a near field optical setup with originally fabricated probes. We performed, for the first time on these samples, near field fluorescence imaging showing evidence that the perylene aggregations actually have a distinct optical orientation.     

Reaction of triphenylphosphine radical cation with cycloalkenes: electrochemical one-step preparation of 1-cycloalkenyltriphenylphosphonium salts

Constant current electrolysis of triphenylphosphine in dichloromethane at a graphite anode in the presence of cycloalkenes gave the corresponding 1-cycloalkenylphosphonium salts in reasonable yields.     

An Isolation and liquid phase EPR spectra of the cation radical salts of N-methyl and N-ethylphenothiazinium perchlorate

N-Methyl and N-ethylphenothiazines were oxidized with bromine and sodium perchlorate to give stable cation radical salts. Their well-resolved epr spectra were obtained in nitromethane solution. In order to assign the hfs constants, the cation radicals of N-deuteriomethyl and N-deuterioethylphenothiazines were prepared with lead tetraacetate and trifluoroacetic acid in solutions.     

Parallel synthesis of tri- and tetrasubstituted ureas from carbamoyl imidazolium salts

A method for producing tri- and tetrasubstituted ureas from carbamoyl imidazolium salts is presented. Carbamoyl imidazolium salts are prepared from the reaction of N,N carbonyldiimidazole (CDI) with secondary amines, followed by alkylation with iodomethane. These stable salts can be stored for extended periods and are effective electrophilic carbamoylation reagents. Primary and secondary amines add to carbamoyl imidazolium salts at room temperature to give tri- and tetrasubstituted ureas in excellent yields. This reaction was used to synthesize ureas using both liquid-liquid extraction and solid-phase extraction (cation exchange) purification techniques. Liquid-liquid extraction affords the product ureas more cleanly than cationic exchange. A series of urea compounds were synthesized using parallel synthesis techniques in high yields and with suitable purity for routine in vitro biological tests. These studies validate the utility of carbamoyl imidazolium salts as useful building blocks for combinatorial library synthesis.     

Pleated polymeric foldamers driven by donor–acceptor interaction and conjugated radical cation dimerization

Two naphthalene(NP) and bipyridinium(BIPY~(2+)) alternately incorporated polymers P1 and P2 have been prepared through the formation of dynamic hydrazone bonds. The polymers formed NP–BIPY~(2+)donor–acceptor interaction-induced pleated secondary structure. Upon reducing the BIPY~(2+)units to radical cation BIPY+, intramolecular dimerization of the BIPY+units induced the backbones to afford another pleated secondary structure. Adding electron-rich macrocyclic polyether bis-1,5-dinaphtho[38]crown-10 or electron-deficient cyclobis(paraquat-p-phenylene) cyclophane did not break the first foldamer by complexing the BIPY2+or NP units of the polymers, whereas the di(radical cationic)ring of the second cyclophane could break the second foldamer by forming threading complexes with the BIPY+units of the polymers.     

The mechanism of the retro-Diels-Alder reaction in 4-vinylcyclohexene cation radical

Butadiene cation radicals are produced symmetrically from the ring and side-chain of the vinylcyclohexene cation radical near the onset of the fragmentation. The appearance energies of C₄H₆^+? and C₄H₂D₄^+? from (3,3,6,6-D₄)vinylcyclohex ene were measured as 11.07 ± 0.05 and 11.06 ± 0.06 eV, respectively. This sets the barrier to retro-Diels-Alder decomposition at 1140 kJ mol^?1 above the energy of 1 and 44 kJ mol^?1 above the thermochemical threshold corresponding to C₄H₆^+? + C₄H₆. Topological molecular orbital calculations indicate that this lowest-energy path involves a sequential rupture of the C₃C₄ and C₅C₆ bonds, with a calculated barrier of 211 kJ mol^?1. The second, two-step reaction channel proceeds by subsequent fission of the C₅C₆ and C₃C₄ bonds with a barrier of 299 kJ mol^?1. This channel is found experimentally as a break on the ionization efficiency curve at 12.1 eV. Both the supra-supra and the supra-antara pericyclic reactions go through energy maxima and are therefore forbidden. The supra-supra process is the most favorable route for decomposition from the first excited state, the activation energy being 333 kJ mol^?1. The preference for the two-step mechanism is due to hyperconjugative stabilization of intermediate molecular configurations.     

Formation of intramolecular poly(4-hydroxystyrene) dimer radical cation

Poly(4-hydroxystyrene) (PHS) has been used in lithography as a backbone polymer and is also a promising material for extreme-ultraviolet or electron beam lithography. The dynamics of PHS radical cations generated upon exposure to electron beam were investigated. The transient absorption of PHS was observed in the near-infrared region in p-dioxane solutions by pulse radiolysis. Charge resonance (CR) bands that represent pi-pi interaction between the two chromophores of the intramolecular PHS dimer radical cation were observed, whereas p-cresol shows no distinct CR band. Although the radical cations of phenol derivatives are known to be easily deprotonated, it was found that the dimer radical cation formation leads to less deprotonation by its charge resonance stabilization.     

The first BETS radical cation salts with dicyanamide anion: Crystal growth, structure and conductivity study

Electrochemical oxidation of bis(ethylenedithio)tetraselenafulvalene (BETS) has been investigated. Simple and complex dicyanamides of transition metals (Mn²⁺, Ni²⁺ and Fe²⁺) were used as electrolytes. The correlation between composition of prepared radical cation salts and metal nature in electrolytes was established. Manganese dicyanamides provide the formation of BETS salts with the {Mn[N(CN)₂]₃}- and [N(CN)₂]-XH₂O anions. When Ni- or Fe-containing electrolytes were used only metalless BETS salts, α″-BETS₂[N(CN)₂]·2H₂O (I) and θ-BETS₂[N(CN)₂]·3.6H₂O (II), formed. Structures and conducting properties of these salts were analyzed. Both salts exhibit layered structure. Conducting radical cation layers have α″ (I)- or θ-type (II). Anion sheets appear as two-dimensional polymer networks of different types. These networks are formed by [N(CN)]₂⁻ anions and water molecules interlinked by hydrogen bonds. Salt I is a semiconductor and II demonstrates resistance drop down to150 K at normal pressure and down to 72 K at ∼0.4 kbar pressure.     

Reaction path calculations for the interaction of the ethylene radical cation with triplet oxygen

UMNDO reaction path calculations for trapping of the ethylene-cation radical with ground state oxygen suggest that formation of a dioxetane radical cation proceeds through the intermediacy of a peroxycation radical. The predicted enthalpy of activation (ΔH? = 13.8 kcal/mol) is consistent with rapid trapping of olefinic cation radicals by triplet oxygen at room temperature.