Conformation and Aromaticity Switching in a Curved Non-Alternant sp2 Carbon Scaffold

A curved sp² carbon scaffold containing fused pentagon and heptagon units ( 1 ) was synthesized by Pd-catalyzed [5+2] annulation from a 3,9-diboraperylene precursor and shows two reversible oxidation processes at low redox potential, accompanied by a butterfly-like motion. Stepwise oxidation produced radical cation 1 ^.+ and dication 1 ²⁺. In the crystal structure, 1 exhibits a chiral cisoid conformation and partial π-overlap between the enantiomers. For the radical cation 1 ^.+, a less curved cisoid conformation is observed with a π-dimer-type arrangement. 1 ²⁺ adopts a more planar structure with transoid conformation and slip-stacked π-overlap with closest neighbors. We also observed an intermolecular mixed-valence complex of 1 ⋅( 1 ^.+)₃ that has a huge trigonal unit cell [( 1 )₇₂(SbF₆)₅₄⋅(hexane)₁₀₁] and hexagonal columnar stacks. In addition to the conformational change, the aromaticity of 1 changes from localized to delocalized, as demonstrated by AICD and NICS(1)_zz calculations.     

Methylviologen cation radiacal,its dimer and complex in various media

Chemical, photochemical and radiolytic reduction of methylviologen, MV²⁺ (1,1'-dimethyl-4,4' -dipiridinum) leads to the formation of methylviologen cation radical, MV ^+.. It is stable in aprotic solvents, dry polymer foils and frozen aqueous solutions. In the presence of water at ambient temperatures MV^+. can undergo oxidation or conversion into dimer (MV^+.)₂ and/or complex MV^+. (MV²⁺). Upon freezing or addition of neutral salt, MV^+. forms dimers in diluted MV²⁺ solutions (below 0.01 mol dm^-3) while in concentrated ones (exceeding 0.05 mol dm^-3) the formation of the complex prevails. Spectral and E.S.R. characteristics of MV^+., its dimer and complex are given.     

Reaction of carotenoids with CCl<Subscript>3</Subscript>OO<Superscript>.</Superscript> by using pulse radiolysis

The interactions of carotenoids (bixin, β-carotene and lycopene) with CCl₃OO^. in aqueous and i-propylalcohol solution saturated with air have been studied by pulse radiolysis. For bixin and β-carotene reaction products from forming process, absorbing in the region of 650 nm, is observed with concomitant carotenoid bleaching (bixin at 500 nm, β-carotene at 450 nm). Their rate constants from forming process are 1.78 ×10⁸ and 7.8 ×10⁷ mol^-1 · L · s^-1 respectively. However, in the case of lycopene, no such a forming process of reaction as bixin and β-carotene can be observed although there is the bleaching reaction (rate constant 4 ×10⁷ mol^-1 · L · s^-1). The results suggest that the carotenoid radical cation and an additional radical are produced in the case of bixin and β-carotene, whereas lycopene undergoes electron transfer with CCl₃OO^., forming cation radical.     

ESR studies on the reactions of sulphite radical anion,SO3.̄−, with nitroalkane compounds in aqueous solutions

The reactions of the sulphite radical anion, SO₃^{$\text{.}\text{?}$?} (generated from the Ti³⁺-H₂O₂-Na₂SO₃ system at pH 9), in aqueous solutions with some nitroalkane compounds were investigated by using a rapid-mixing flow technique coupled with electron spin resonance (ESR) which can detect the radicals having a lifetime of 5–100 ms. The SO₃^{$\text{.}\text{?}$?} radical added to the double bond of CN in the nitroalkane aci-anions which are the main form of nitroalkanes in aqueous alkaline solutions. From the observed hyperfine splitting constants of the SO₃^{$\text{.}\text{?}$?} adducts of nitroalkane aci-anions, the preferred conformation of the adducts was deduced.     

para‐Phenylene‐Bridged Spirobi(triarylamine) Dimer with Four Perpendicularly Linked Redox‐Active π Systems

para‐Phenylene‐bridged spirobi(triarylamine) dimer 2 , in which π conjugation through four redox‐active triarylamine subunits is partially segregated by the unique perpendicular conformation, was prepared and characterized by structural, electrochemical, and spectroscopic methods. Quantum chemical calculations (DFT and CASSCF) predicted that the frontier molecular orbitals of 2 are virtually fourfold degenerate, so that the oxidized states of 2 can give intriguing electronic and magnetic properties. In fact, the continuous‐wave ESR spectroscopy of radical cation 2 ^.+ showed that the unpaired electron was trapped in the inner two redox‐active dianisylamine subunits, and moreover was fully delocalized over them. Magnetic susceptibility measurements and pulsed ESR spectroscopy of the isolated salts of 2 , which can be prepared by treatment with SbCl₅, revealed that the generated tetracation 2 ⁴⁺ decomposed mainly into a mixture of 1) a decomposed tetra(radical cation) consisting of a tri(radical cation) moiety and a trianisylamine radical cation moiety (≈75 %) and 2) a diamagnetic quinoid dication in a tetraanisyl‐p‐phenylendiamine moiety and two trianisylamine radical cation moieties (≈25 %). Furthermore, the spin‐quartet state of the tri(radical cation) moiety in the decomposed tetra(radical cation) was found to be in the ground state lying 30 cal mol^?1 below the competing spin‐doublet state.     

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(CF₃)₃) or SbF₆^?. They were prepared by reaction of the respective silver(I) salts with stoichiometric amounts of benzidine or its alkyl‐substituted derivatives in CH₂Cl₂. 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 ^{. +}SbF₆^? 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.     

A further understanding of the cation exchange mechanism for the extraction of Sr2+ and Cs+ by ionic liquid

The cation exchange mechanism was further investigated during the extraction of Sr 2+ and Cs+ using the extractant dicyclo- hexano-18-crown-6 (DCH18C6) in an ionic liquid (IL)1-ethyl-3-methyimidazolium bis[(trifluoromethyl)sulfonyl]imide (C2 mimNTf2 ). The concentrations of both the cation C2 mim + and the anion NTf2 in aqueous phase were detected. The con-centration of NTf2 in the aqueous phase decreased as Sr2+ or Cs+ exchanged into the IL phase. Addition of C2 mim + or NTf2 as well as the variation of the solubility of C2 mimNTf2 influenced the extraction efficiency of Sr2+ or Cs+ .     

Photoinduced Interactions Between Oxidized and Reduced Lipoic Acid and Riboflavin (Vitamin B2)

As a powerful natural antioxidant, lipoic acid (LipSS) and its reduced form dihydrolipoic acid (DHLA) exert significant antioxidant activities in vivo and in vitro by deactivation of reactive oxygen and nitrogen species (ROS and RNS). In this study the riboflavin (RF, vitamin B₂) sensitized UVA and visible‐light irradiation of LipSS and DHLA was studied employing continuous irradiation, fluorescence spectroscopy, and laser flash photolysis (LFP). Our results indicate that LipSS and DHLA quench both the singlet state (¹RF*) and the triplet state (³RF*) of RF by electron transfer to produce the riboflavin semiquinone radical (RFH^.) and the radical cation of LipSS and DHLA, respectively. The radical cation of DHLA is rapidly deprotonated twice to yield a reducing species; the radical anion of LipSS (LipSS^.?). When D₂O was used as solvent, it was confirmed that the reaction of LipSS with ³RF* consists of a simple electron‐transfer step, while loss of hydrogen occurs in the case of DHLA oxidation. Due to the strong absorption of RFH^. and the riboflavin ground state, the absorption of the radical cation and the radical anion of LipSS can not be observed directly by LFP. N,N,N′,N′‐tetramethyl‐p‐phenylenediamine (TMPD) and N,N,N′,N′‐tetramethyl benzidine (TMB) were added as probes to the system. In the case of LipSS, the addition resulted in the formation of the radical cation of TMPD or TMB by quenching of the LipSS radical cation. If DHLA is the reducing substrate, no formation of probe radical cation is observed. This confirms that LipSS^.+ is produced by riboflavin photosensitization, and that there is no oxidizing species produced after DHLA oxidization.     

Sorption of transition metal cations on natural heulandite

The cation exchange equilibrium in the systems of natural heulandite-binary aqueous solutions of NaCl, NiCl₂, CuCl₂, ZnCl₂, and MnCl₂ was studied. The corrected coefficients of the selectivity (k ^a _M/Na) and thermodynamic constants (K _M/Na) of the cation exchange of Na⁺ cations for transition metal cations were determined. The selectivity of the cation exchange on natural heulandite increases in the following order: Ni²⁺ < Cu²⁺ < Zn²⁺ < Na²⁺ < Mn²⁺.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1101–1103, May, 1996.     

Radical‐Cation Dimerization Overwhelms Inclusion in [n]Pseudorotaxanes

Suppression of the dimerization of the viologen radical cation by cucurbit[7]uril ( CB7 ) in water is a well‐known phenomenon. Herein, two counter‐examples are presented. Two viologen‐containing thread molecules were designed, synthesized, and thoroughly characterized by ¹H DOSY NMR spectrometry, UV/Vis absorption spectrophotometry, square‐wave voltammetry, and chronocoulometry: BV ⁴⁺, which contains two viologen subunits, and HV ¹²⁺, which contains six. In both threads, the viologen subunits are covalently bonded to a hexavalent phosphazene core. The corresponding [3]‐ and [7]pseudorotaxanes that form on complexation with CB7 , that is, BV ⁴⁺?( CB 7)₂ and HV ¹²⁺?( CB 7)₆, were also analyzed. The properties of two monomeric control threads, namely, methyl viologen ( MV ²⁺) and benzyl methyl viologen ( BMV ²⁺), as well as their [2]pseudorotaxane complexes with CB7 ( MV ²⁺? CB7 and BMV ²⁺? CB7 ) were also investigated. As expected, the control pseudorotaxanes remained intact after one‐electron reduction of their viologen‐recognition stations. In contrast, analogous reduction of BV ⁴⁺?( CB 7)₂ and HV ¹²⁺?( CB 7)₆ led to host–guest decomplexation and release of the free threads BV ^{2( . +)} and HV ^{6( . +)}, respectively. ¹H DOSY NMR spectrometric and chronocoulometric measurements showed that BV ^{2( . +)} and HV ^{6( . +)} have larger diffusion coefficients than the corresponding [3]‐ and [7]pseudorotaxanes, and UV/Vis absorption studies provided evidence for intramolecular radical‐cation dimerization. These results demonstrate that radical‐cation dimerization, a relatively weak interaction, can be used as a driving force in novel molecular switches.     

Separation of different ion structures in atmospheric pressure photoionization-ion mobility spectrometry-mass spectrometry (APPI-IMS-MS)

This study demonstrates how positive ion atmospheric pressure photoionization-ion mobility spectrometry-mass spectrometry (APPI-IMS-MS) can be used to produce different ionic forms of an analy te and how these can be separated. When hexane:toluene (9:1) is used as a solvent, 2,6-di-tert-butylpyridine (2,6-DtBPyr) and 2,6-di-tert-4-methylpyridine (2,6-DtB-4-MPyr) efficiently produce radical cations [M]⁺ and protonated [M + H]⁺ molecules, whereas, when the sample solvent is hexane, protonated molecules are mainly formed. Interestingly, radical cations drift slower in the drift tube than the protonated molecules. It was observed that an oxygen adduct ion, [M + O₂]⁺, which was clearly seen in the mass spectra for hexane:toluene (9:1) solutions, shares the same mobility with radical cations, [M]⁺. Therefore, the observed mobility order is most likely explained by oxygen adduct formation, i.e., the radical cation forrning a heavier adduct. For pyridine and 2-tert-butylpyridine, only protonated molecules could be efficiently formed in the conditions used. For 1- and 2-naphthol it was observed that in hexane the protonated molecule typically had a higher intensity than the radical cation, whereas in hexane:toluene (9:1) the radical cation [M]⁺ typically had a higher intensity than the protonated molecule [M + H]⁺. Interestingly, the latter drifts slower than the radical cation [M]⁺, which is the opposite of the drift pattern seen for 2,6-DtBPyr and 2,6-DtB-4-MPyr.     

Deamination of the Radical Cation of the Base Moiety of 2′‐Deoxycytidine: A Theoretical Study

Five pathways leading to the deamination of cytosine (to uracil) after formation of its deprotonated radical cation are investigated in the gas phase, at the UB3LYP/6‐311G(d,p) level of theory, and in bulk aqueous solvent. The most favorable pathway involves hydrogen‐atom transfer from a water molecule to the N3 nitrogen of the deprotonated radical cation, followed by addition of the resulting hydroxyl radical to the C4 carbon of the cytosine derivative. Following protonation of the amino group (N4), the C4? N4 bond is broken with elimination of the NH₃^?+ radical and formation of a protonated uracil. The rate‐determining step of this mechanism is hydrogen‐atom transfer from a water molecule to the cytosine derivative. The associated free energy barrier is 70.2 kJ mol^?1.     

The structure and dissociation pathways of protonated methanol: An ab initio molecular orbital study

Ab initio molecular orbital calculations with moderately large polarization basis sets and including valence-electron correlation have been used to examine the structure and dissociation mechanisms of protonated methanol [CH₃OH₂]⁺. Stable isomers and transition structures have been characterized using gradient techniques. Protonated methanol is found to be the only stable isomer in the [CH₅O]⁺ potential surface. There is no evidence for a tightly-bound complex, [HOCH₂]⁺…?H₂, analogous to the preferred structure [CH₃]⁺…?H₂ of [CH₅]⁺. Protonated methanol is found to possess a pyramidal arrangement of bonds at the oxygen atom with a barrier to inversion of 8kJ mol^?1. The lowest energy fragmentation pathways are dissociation into methyl cation and water (predicted to require 284 kJ mol^?1 with zero reverse activation energy) and loss of molecular hydrogen (endothermic by 138 kJ mol^?1 but with a reverse activation barrier of 149 kJ mol^?1). The results offer a possible explanation as to why production of [CH₂OH]⁺ from the reaction of methyl cation with water is not observed. Other dissociation processes examined include loss of a hydrogen atom to yield the methylenoxonium radical cation or methanol radical cation (requiring 441 and 490 kJ mol^?1, respectively) and loss of a proton to yield neutral methanol (requiring 784 kJ mol^?1).     

Proton Transfer Accompanied by the Oxidation of Adenosine

Despite numerous experimental and theoretical studies, the proton transfer accompanying the oxidation of 2′-deoxyadenosine 5′-monophosphate 2’-deoxyadenosine 5’-monophosphate (5’-dAMP, A ) is still under debate. To address this issue, we have investigated the oxidation of A in acidic and neutral solutions by using transient absorption (TA) and time-resolved resonance Raman (TR³) spectroscopic methods in combination with pulse radiolysis. The steady-state Raman signal of A was significantly affected by the solution pH, but not by the concentration of adenosine (2–50 mm ). More specifically, the A in acidic and neutral solutions exists in its protonated ( A H⁺(N1+H⁺)) and neutral ( A ) forms, respectively. On the one hand, the TA spectral changes observed at neutral pH revealed that the radical cation ( A ^.+) generated by pulse radiolysis is rapidly converted into A ^.(N6−H) through the loss of an imino proton from N6. In contrast, at acidic pH (<4), A H^.2+(N1+H⁺) generated by pulse radiolysis of A H⁺(N1+H⁺) does not undergo the deprotonation process owing to the pK_a value of A H^.2+(N1+H⁺), which is higher than the solution pH. Furthermore, the results presented in this study have demonstrated that A , A H⁺(N1+H⁺), and their radical species exist as monomers in the concentration range of 2–50 mm . Compared with the Raman bands of A H⁺(N1+H⁺), the TR³ bands of A H^.2+(N1+H⁺) are significantly down-shifted, indicating a decrease in the bond order of the pyrimidine and imidazole rings due to the resonance structure of A H^.2+(N1+H⁺). Meanwhile, A ^.(N6−H) does not show a Raman band corresponding to the pyrimidine+NH₂ scissoring vibration due to diprotonation at the N6 position. These results support the final products generated by the oxidation of adenosine in acidic and neutral solutions being A H^.2+(N1+H⁺) and A ^.(N6−H), respectively.     

ESR.-Studies of Nonalternant Radicals Structurally Related to Phenalenyl

The radical anion and the radical cation of azuleno[1,2,3-cd]phenalene (III) have been investigated by ESR. spectroscopy, along with the radical anion of 2-phenylazulene (IV). Also studied has been the neutral radical obtained by one-electron reduction of cyclohepta[cd]phenalenium-cation (VI^⊕). Assignment of the proton coupling constants for the radical ions III. ·?, III ·⊕ and IV·⊕, and the radical VI · is supported by comparison with the ESR. spectra of specifically deuteriated derivatives III-d₅ ·?, III-d₅ ·⊕, IV-d₂ ·? and VI-d₁′. The experimental results are in full accord with qualitative topological arguments and predictions of HMO models. Whereas the radical anion III ·? exhibits α-spin distribution similar to that of IV ·?the corresponding radical cation III ·⊕ and the neutral radical VI · are related in this respect to phenalenyl (V·). It is noteworthy that oxidation of III by conc. H₂SO₄ yields a paramagnetic species (IIIa ·⊕) which has a similar – but not an identical – structure as the radical cation III ·⊕ produced from III with AlCl₃ in CH₃NO₂.     

(2-Chlorobenzyl)tris(2-pyridinethiolato)tin(IV)

In the title compound, (2-chloro­benzyl)­tris­(pyridine-2-thiol­ato)-κ²N,S;κ²N,S;κS-tin(IV), [Sn(C₇H₆Cl)(C₅H₄NS)₃], two of the three pyridine-2-thiol­ato ligands (SPy) are bidentate and one is monodentate. The bonding C atom of the 2-chloro­benzyl group, the S atom of the monodentate SPy and the S and N atoms of the two bidentate SPy ligands form a distorted octahedron around the Sn atom. The three S atoms and the N atom of one of the bidentate SPy ligands occupy the equatorial positions, while the N atom of the second bidentate SPy ligand and the C(CH₂) atom are axial. The axial N—Sn—C angle of 157.9 (1)° demonstrates the heavy distortion of the octahedron.     

Time resolved absorption and resonance Raman spectroscopic studies of the oxidation of benzidine in aqueous solution

We report a time resolved resonance Raman study of transient radicals produced in the pulse radiolytic oxidation of benzidine in aqueous solution. The intense and structured transient absorption in the 400–470 nm region, observed at microsecond times in the acidic medium, is attributed to the benzidine radical cation. The Raman spectrum, observed by excitation in resonance with this absorption, exhibits eight prominent bands which are assigned to planar phenyl vibrations. The ring breathing mode (v₁) at 844 cm^-1 is most highly resonance enhanced, indicating an overall expansion of the ring CC bonds in the excited state. The interring CC bond, with partial double bond character, is characterized by an intense (v₁₃) Raman band at 1335 cm^-1. The frequency of the in-phase v_7a CN stretching vibration is 1540 cm^-1. These frequencies and the presence of weak bands attributable to non-planar phenyl vibrations indicate the radical to be slightly non-planar. The pK_a for the proton loss from the radical cation is 10.87, four units higher than for the aniline radical cation. At high pH the observed transient has a broad and structureless absorption at ∽ 380 nm. It is identified from its resonance Raman features as the 4(4′aminophenyl)anilino radical formed by proton loss from the radical cation. The interring CC bond is characterized by a Raman band at 1292 cm^-1, indicating it to be a single bond. The structure of this neutral radical is highly nonplanar, with little conjugation between the two ring systems so that electronic excitation is primarily confined to the anilino moiety. The acidic and basic forms of the radical react rapidly in second order processes to produce products which absorb strongly at, respectively, 360 and 410 nm.     

Ab initio MO calculations on the stable conformations and their binding energies of the ion-molecule complexes: Ion = H+, Li+, Na+, K+ Be2+, and molecule = CO and N2

The most stable conformation of ion-molecule complexes involving a CO molecule were surveyed by the use of Hartree-Fock (HF) MO and third-order Moller-Plesset perturbation (MP3) methods with a 6–31G* basis set ion = H⁺, Li⁺, Na⁺, K⁺, Bc²⁺, Mg²⁺, and Ca²⁺. The MP3 level of theory reveals the ion-CO conformation in which the ion bonds to a carbon atom of CO to be the most stable; these MP3 results are contrary to the HF ones. Binding energies of ion-molecule complexes involving CO and N₂ were computed; MP3 energies are in good agreement with the experimental ones. The computed binding energies of cation-N₂ are about one-third of cation-NH₃ due to the absence of dipole moment and the smaller polarizability of N₂. The decrease in binding energy in cation-CO and -N₂ complexes, with increasing cation size, is mainly caused by the decrease of the electrostatic and polarization stabilizations.     

On the ionic states of vinylidene and acetylene

Electronic states of C₂H⁺₂ cation (with acetylenic and vinylidenic structure) are investigated by ab initio SCF and PNO CEPA calculations. The lowest excited state of the acetylene cation is calculated to be ⁴A₂ in a strongly bent cis conformation, and a qualitative explanation is given for the lack of detectable emission from theò∑_g⁺ state. Only the radical anion with the vinylidenic structure is bound.     

Spectroscopic characterization of mechanisms of oxidation of Phe by SO4- radical: A pulse radiolysis study

By using time-resolved kinetic spectrophotometry and pulse radiolysis technique, the oxidation of Phe by SO₄ ^- radical has been investigated both in aqueous and water/acetonitrile mixed solutions. The results reveal that attack of the oxidizing SO₄ ^- radical on Phe leads directly to the formation of Phe cation radical 3 with a strong absorption peak at 310 nm, then it proceeds in three competitive reactions via either hydroxylation, deprotonation or decarboxylation, which were found to be strongly dependent upon the ionization state of the substitutes —COOH and —NH₂ and the nature of the solvents. Decarboxylation takes place only when the carboxyl group is deprotonated. At high pH deprotonation of Phe cation radical 3 is much easier to occur than that in neutral or acid solutions. Moreover, with addition of acetonitrile, deprotonation is more predominant than hydroxylation, whereas in aqueous solutions hydroxylation is much easier to occur.