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1.
The kinetics of charge recombination in radical ion pairs C70 /Am+ (Am isN, N, NN-tetramethyl-p-phenylenediamine,p-methoxy-N,N-dimethylaniline,p-methyl-N,N-di-methylaniline,N,N-diethylaniline,N,N-dimethylaniline, and triphenylamine) in chlorobenzene was studied by the picosecond laser photolysis technique. The radical ion states are the products of excitation of charge-transfer complexes between C70 and amines and are also formed by quenching of the singlet excited state of C70 by the amine. The rate constant of electron transfer in the radical ion pair decreases as the free Gibbs energy (G) of the reaction increases and reflects the Marcus-inverted region of the dependence of the rate constant on G. The C70/Am and C60/Am systems are compared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1151–1158, May, 1996.  相似文献   

2.
Efficiencies and rates of electron transfer from various electron donors to excited fullerenes (C60 and C70) have been determined by observing the transient absorption bands in the near-IR region, where the anion radicals of fullerenes appear. From the rise of the absorption bands of C60 −+ and C70 −+ in the near-IR region, electron transfer takes place via the triplet states (TC60 * and TC70 *) under appropriately low concentrations of electron donors. By analysis of the rise curves C60 −+ and C70 −+, contribution of the excited singlet states (SC60 * and SC70 *) in addition to the route of the triplet states (TC60 * and TC70 *) is confirmed. The quantum yield for electron transfer via the triplet states Φct T was evaluated by the ratio of [C60 −+]/[TC60 *] (or [C70 −+/[TC70 *]). The Φct T depends upon the donor-ability, donor concentration, and solvent polarity. The back electron-transfer process, which was evaluated by observing C60 −+, also depends upon the solvent polarity.  相似文献   

3.
Pulse radiolysis of acetonitrile solutions of tetra-n-butyl ammonium salts of 2- and 4-carboxybenzophenones [BP-COO···N+(C4H9)4] were performed in order to generate directly the reduced forms of the benzophenone moieties within pre-formed ion pairs. In earlier studies on photochemical electron transfer reactions, ion pairs containing a tetraalkyl ammonium cation and a benzophenone radical anion were formed in an electron transfer to the triplet BP from a quencher consisting of a tetraalkyl ammonium salt of (phenylthio)acetic acid. In the current work, the [BP•−COO···N+(C4H9)4] ion pairs were formed by direct reduction of the salts without the complication of a third moiety, i.e., the (phenylthio)acetic anion. The spectra and kinetic parameters of the radiolytically-reduced salts were compared to the behavior of reduced forms of the 2- and 4-COOH substituted benzophenones. The results from the pulse radiolysis and photochemistry were compared and explained in terms of the different structures of the ion pairs.  相似文献   

4.
The interaction between the radical anions C60 ·− and divalent d- and f-metal (Co, Fe, Ni, Mn, Eu, Cd) cations in DMF and acetonitrile-benzonitrile (AN-BN) mixture was studied. Black solid polycrystalline salts (C60 ·−)2{(M2+)(DMF) x } (x = 2.4–4, 1–6) containing the radical anions C60 ·− and metal(ii) cations solvated by DMF were prepared for the first time and their optical and magnetic properties were studied. The salts containing Co2+, Fe2+, and Ni2+ are characterized by antiferromagnetic interactions between the radical anions C60 ·−, which result in unusually large broadening of the EPR signal of C60 ·− upon lowering the temperature (from 5.55–12.6 mT at room temperature to 35–40 mT at 6 K for Co2+ and Ni2+). The salts containing Mn2+ and Eu2+ form diamagnetic dimers (C60 )2, which causes a jumpwise decrease in the magnetic moment of the complexes and disappearance of the EPR signal of C60 ·− in the temperature range 210–130 K. A feature of salt 6 is magnetic isolation of the radical anions C60 ·− due to the presence of diamagnetic cation Cd2+. The salts prepared are unstable in air and decompose in o-dichlorobenzene or AN. Reactions of C60 ·− with metal(ii) cations in AN-BN mixture result in decomposition products of the salts that contain neutral fullerene dimers and metals solvated by BN. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1909–1919, September, 2008.  相似文献   

5.
The interaction of molecular oxygen with aqueous trifluoroacetic acid (TFA) led to an increase in pH. This effect was explained by a decrease in the concentration of the protonated CF3CO2H2+ and H3O+ species after oxygen was fed in the reactor. Quantum-chemical calculations show that a radical pair can be formed in an activation-free exothermal reaction involving the radical residue of the acid, the CF3CO2H2+...3O2...CF3CO2 peroxide radical, and the acid molecule in the CF3C2·...HOO· collision complex. It was assumed that the activation of molecular oxygen in aqueous TFA solutions, providing the activity of the system in oxidations of various organic and inorganic substrates, is related to the formation of peroxide radicals in them.  相似文献   

6.
The mechanism of the photoinduced reaction of the lowest excited singlet state of the 10-methylacridinium (AcrMe+) cation with benzyltrimethylsilane (BTMSi) in acetonitrile has been investigated by means of steady-state and time-resolved methods. A variety of stable products was found after irradiation (365 nm) of the reaction mixture under aerobic and oxygen-free conditions. The stable products were identified and analyzed using UV–Vis spectrophotometry, high performance liquid chromatography (HPLC), and mass spectrometry (MS). Based on Stern–Volmer plots of the AcrMe+ fluorescence quenching by BTMSi (using fluorescence intensity and lifetime measurements), the rate constants were determined to be k q = 1.24 (± 0.02) × 1010 M−1 s−1 and k q = 1.23 (± 0.02) × 1010 M−1 s−1, i.e., close to the diffusion-controlled limit in acetonitrile, indicating the dynamic quenching mechanism. The quenching process was shown to occur via an electron-transfer reaction leading to the formation of acridinyl radicals (AcrMe) and C6H5CH2Si(CH3)3 •+ radical cations. Based on stationary and flash photolysis experiments, a detailed mechanism of the secondary reactions is proposed and discussed. The AcrMe radical was shown to decay by two processes. The fast decay, observed on the nanosecond timescale, was attributed to the back-electron transfer occurring within the initial radical ion pair. The slow decay on the microsecond timescale was explained by recombination reactions of radicals which escaped from the radical pair, including benzyl radicals formed via C–Si bond cleavage in the C6H5CH2Si(CH3)3 •+ radical cation.  相似文献   

7.
The reaction of the · OH radical with the oxalate ion in an acidic aqueous solution was studied by pulse radiolysis. The rate constant for the reaction of formation of the radical HOOC-COO·(λmax = 250 nm, ɛ = 1800 L mol−1 cm−1) is (5.0±0.5)·107 L mol−1 s−1. In the reaction with the hydrogen ion (k = 1.1·107 L mol−1 s−1), the radical HOOC-COO· is transformed into a nonidentified radical designated arbitrarily as H+(HOOC-COO)· (λmax = 260 nm, ɛ = 4000 L mol−1 cm−1). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1165–1167, June, 2008.  相似文献   

8.
The [60]fulleride of bis(η-hexamethylbenzene)chromium(I) [(η6-C6Me6)2Cr]⋅+[C60]⋅−, and the complexes C60·C6Me6 and C60·C6Et6 were synthesized. Thermal decomposition of [(η6-C6Me6)2Cr]⋅+[C60]⋅− was studied. The molecular structures of C60·C6Me6 and C60·C6Et6 were determined. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 220—224, February, 2006.  相似文献   

9.
Radical-ion salts bis(biphenyl)chromium(i) 1,4-di(2-cyanoisopropyl)-1,4-dihydrofulleride [(Ph2)2Cr][1,4-(CMe2CN)2C60]−· and bis(biphenyl)chromium(i) 1-(2-cyanoisopropyl)-1,2-dihydrofulleride [(Ph2)2Cr][1,2-(CMe2CN)(H)C60]−·, the salt bis(biphenyl)chromium(i) (2-cyanoisopropyl)fulleride [(Ph2)2Cr][(CMe2CN)C60], and neutral 1-(2-cyanoisopropyl)-1,2-dihydrofullerene 1,2-(CMe2CN)(H)C60 have been synthesized for the first time. The compounds [(Ph2)2Cr][1,4-(CMe2CN)2C60]−· and [(Ph2)2Cr][1,2-(CMe2CN)(H)C60]−· decompose in THF to form [(Ph2)2Cr][(CMe2CN)C60], whose protonation affords 1,2-(CMe2CN)(H)C60. 1,4-Di(2-cyanoisopropyl)-1,4-dihydrofullerene 1,4-(CMe2CN)2C60 and 1,2-(CMe2CN)(H)C60 are stable in vacuo up to 513 K. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1935–1939, September, 2008.  相似文献   

10.
The temperature dependence of the heat capacity of crystalline bis-(η6-ethoxybenzene)chromium fulleride [(η6-(EtOPh))2Cr]·+[C60]·− was studied for the first time by adiabatic vacuum calorimetry over the temperature range 6–340 K with errors of ±0.2%. The temperature dependence of the EPR signal parameters of bis-(η6-ethoxybenzene)chromium fulleride was studied for the first time from 120 to 340 K. A reversible endothermic transformation was observed between 160 and 250 K during heating; it was caused by the dissociation of the [(C60)2]2− dimer and the formation of the [(η6-(EtOPh))2Cr]·+[C60]·− fulleride; its standard thermodynamic characteristics were estimated and analyzed. The experimental data were used to calculate the standard thermodynamic functions, including the heat capacity, enthalpy, entropy, and Gibbs function of the fulleride dimer from T → 0 to 160 K and the [(η6-(EtOPh))2Cr]·+[C60]·− monomeric complex over the temperature range 250–340 K. The standard thermodynamic properties of the fulleride studied, fullerides studied earlier, and fullerite C60 were compared.  相似文献   

11.
Electrochemistry of hydrofullerene C60H36 was studied by cyclic voltammetry in THF and CH2Cl2 in the −47–14 °C temperature range. Hydrofullerene undergoes reversible one-electron reduction to form a radical anion in THF (E 0=−3.18 V (Fc0/Fc+), Fc=ferrocene) and irreversible one-electron oxidation in CH2Cl2 (E p a =1.22 V (Fc0/Fc+)). The reduction potential was used to estimate electron affinity of hydrofullerene as EA=−0.33 eV. It was suggested that C60H36 is an isomer withT-symmetry in which 12 double bonds form four isolated benzenoid rings located in vertices of an imaginary inscribed tetrahedron on the molecular surface. For hydrofullerene, the “electrochemical gap” is an analog of the energy gap (HOMO−LUMO), equal to (E OxE Red)=4.4 V, and indicates that C60H36 is a sufficiently “hard” molecule with a low reactivity in redox reactions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2083–2087, November, 1999.  相似文献   

12.
The temperature dependence of heat capacity of crystalline bis(η6-ethylbenzene)chromium fulleride [(η6-EtPh)2Cr]·+ [C60]·− was studied in adiabatic vacuum calorimeter in the range of 6.7 to 344 K with an error of ±0.3%. Dependence of the parameters of EPR signal of bis(η6-ethylbenzene)chromium fulleride on temperature was studied by electron paramagnetic resonance (EPR) in the range of 120 to 290 K. In the range of 204 to 246 K, upon heating, reversible endothermic transformation was recorded, which is caused by the dissociation of dimer (C60)2 and formation of fulleride [(η6-EtPh)2Cr]·+ [C60]·−; its standard thermodynamic parameters were estimated and analyzed. Standard thermodynamic functions were calculated by the experimental data obtained: heat capacity, enthalpy, entropy, and Gibbs function of fulleride dimmer in the range of T → 0 to 204 K and monomer complex [(η6-EtPh)2Cr]·+ [C60]·− in the range of 246 to 344 K. Standard thermodynamic properties of fulleride under study, fullerides studied earlier, and fullerite C60 were compared.  相似文献   

13.
Axial coordination of fullerenopyrrolidine bearing the donor imidazolyl group, cis-3-(4-imidazolylphenyl)-1-(pyridin-2-yl)[60]fullereno[1,2-c]pyrrolidine (C60∼Im), with zinc meso-tetraphenylporphyrinate (ZnTPP) in an o-dichlorobenzene solution affords a non-covalently bonded donor-acceptor dyad ZnTPP-C60∼Im. The photochemical behavior of the ZnTPP-C60∼Im complex was studied by fluorescence (excitation at λ = 420 nm) and laser kinetic spectroscopy (excitation at λ = 532 nm, 12 ns). The formation constant of the 1: 1 porphyrin-fullerenopyrrolidine complex determined from quenching of ZnTPP fluorescence assuming static intracomplex quenching is 1.6·104 L mol−1. Absorption spectra of the excited states in the system consisting of ZnTPP and Im∼C60 (ZnTPP/C60∼Im) were measured in solution from 380 to 1000 nm. The quenching constant of the triplet-excited ZnTPP with fullerenopyrrolidine C60∼Im was determined. The results obtained indicate the formation of the triplet exciplex {PL}* ⇌ {Pδ+…Lδ−} in the ZnTPP/C60∼Im system upon laser photolysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1541–1547, September, 2006.  相似文献   

14.
The problem of existence of η5-π-complexes of unsubstituted fullereneI h -C60 and its cyclopentadienyl type derivative C60H5 . is discussed.Ab initio MO LCAO SCF calculations of hypothetical sandwich systems η5-π-C60H5XCp (X=Fe (1a), Si (1b)), the cationic complex C60FeCp+ of unsubstituted C60, and the C60H5 . radical were performed in the STO-3G and 3-21G basis sets. In the1a, 1b, and C60H5 . systems, hydrogen atoms are attached to carbon atoms of fullerenei h -C60 at α-positions relative to the same pentagonal face (pent *). In η5-complexes, XCp species are also coordinated to this face. According to calculations in the 3-21G basis set, the Fe-pent * bond energy in complex1a is much higher than those of similar bonds in1b and in the η5-π-C60FECp+ cation (117 kcal mol−1 vs. 37 and 64 kcal mol−1, respectively) and is 7 kcal mol−1 higher than the Fe−Cp bond energy in the classical sandwich system FeCp2. The Fe…C pent* and Fe…CCp distances in complex1a are slightly shorter than the Fe…C distance in the ferrocene molecule. The spin populations in the C60H5 . radical are almost completely localized on the atoms of thepent * face, which must favor the formation of η5-π-complexes of this radical. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1657–1662, September, 1999.  相似文献   

15.
Fullerols of C60 and of C70 [C60(OH)n, C70(OH)m], water-soluble fullerene derivatives, unlike some other fullerene derivatives (such as C60 (C4H6O), C60 (C3H7N) and C60 [C(COOEt)2]x), do not result in excited triplet state but in ionization via monophotonic process in aqueous solutions with 248 nm laser. The quantum yields of formation of hydrated electron (Φe ) are determined to be 0.08 and 0.11 for fullerols of C60 and of C70 respectively at room temperature (ca. 15°C) with KI solution used as reference. By laser flash photolysis and oxidation of sulfate radical anion SO4 , the fullerol radical cation or neutral radical of C60 is confirmed to be existent and the transient absorption spectra of fullerol radical cation of C70 are observed for the first time. Project supported by the National Natural Science Foundation of China  相似文献   

16.
Fullerenyl radicals (FR) RC60 · and chemiluminescence (CL) are generated in the presence of O2 in C60—R3Al (R = Et, Bui) solutions in toluene (T = 298 K). The FR are formed due to the addition of the R· radical, which is an intermediate of R3Al autooxidation, to C60. Mass spectroscopy and HPLC were used to identify EtnC60Hm (n, m = 1–6), EtpC60 (p = 2–6), and dimer EtC60C60Et as stable products of FR transformations. As found by ESR, the EtC60 · radical (g = 2.0037) is also generated by photolysis of solutions obtained after interaction in the (C60— R3Al)—O2 system. In the presence of dioxygen, the FR is not oxidized but yields complexes with O2, which appear as broadening of the ESR signals. Chemiluminescence arising in the (C60—R3Al)—O2 system is much brighter (I max = 1.86·108 photon s−1 mL−1) than the known background CL (I max = 6.0·106 photon s−1 mL−1) for the autooxidation of R3Al and is localized in a longer-wavelength spectral region (λmax = 617 and 664 nm). This CL is generated as a result of energy transfer from the primary emitter 3CH3CHO* to the products of FR transformation: RnC60Hm, RpC60, and EtC60C60Et. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 205–213, February, 2007.  相似文献   

17.
Summary.  The distribution of tetraalkylammonium ions (C n H 2n+1 )4N+ (R +, TAAn +, n = 4–7) with picrate ion (pic ) and inorganic anions X , (Cl, Br, ClO 4), into various inert organic solvents was studied at 25.0°C. The distribution data were analyzed by taking into consideration the distribution of ion pairs, R + · X , and the dimerization of the ion pairs, (R + · X )2, in the organic phase. The ion-pair, distribution constant, K dist, increases with increasing chain length of the tetraalkylammonium ion and with increasing ionic radius of the anion. The values of K dist show a good correlation with the E T value of solvent, i.e. the solvation ability with respect to the anion, and smoothly increase with increasing E T. The effect of the solvent on the dimerization constants, K dim, is markedly different between the ion pairs of picrate ion and inorganic anions. In the case of picrate, K dim significantly decreases with decreasing length of the alkyl chain of the tetraalkylammonium ion, but hardly changes by changing the solvent. On the other hand, in the case of ion pairs of inorganic anions the value of K dim decreases with decreasing E T and is almost constant for all anions. These results were reasonably explained by the difference of the solvation of the anion moieties of the monomeric and dimeric ion pairs. Received May 15, 2001. Accepted (revised) July 18, 2001  相似文献   

18.
Pulsed laser excitation of pyrene (P)/N, N-diethylaniline (DEA) solutions in methanol at low temperatures leads to the generation of the P? and DEA+ radical ions. A fast initial decay of the ions (τ12 ≈ 37 nsec at ?40°C) is observed and is attributed to geminate recombination within the initially formed (2P?2DEA+) ion pair. The quenching of 1P*) by DEA is also associated with substantial intersystem crossing, yielding 3P*. The data rule out both gemiate and non-geminate (homogeneous) inonic recombinations as sources for the initial yield of 3P*, in keeping with a prompt triplet formation mechanism.  相似文献   

19.
 The distribution of tetraalkylammonium ions (C n H 2n+1 )4N+ (R +, TAAn +, n = 4–7) with picrate ion (pic ) and inorganic anions X , (Cl, Br, ClO 4), into various inert organic solvents was studied at 25.0°C. The distribution data were analyzed by taking into consideration the distribution of ion pairs, R + · X , and the dimerization of the ion pairs, (R + · X )2, in the organic phase. The ion-pair, distribution constant, K dist, increases with increasing chain length of the tetraalkylammonium ion and with increasing ionic radius of the anion. The values of K dist show a good correlation with the E T value of solvent, i.e. the solvation ability with respect to the anion, and smoothly increase with increasing E T. The effect of the solvent on the dimerization constants, K dim, is markedly different between the ion pairs of picrate ion and inorganic anions. In the case of picrate, K dim significantly decreases with decreasing length of the alkyl chain of the tetraalkylammonium ion, but hardly changes by changing the solvent. On the other hand, in the case of ion pairs of inorganic anions the value of K dim decreases with decreasing E T and is almost constant for all anions. These results were reasonably explained by the difference of the solvation of the anion moieties of the monomeric and dimeric ion pairs.  相似文献   

20.
The possibility of hydrogen transfer from hydrofullerene C60H36 to electrogenerated radical anion C60 .− or dianion C60 2− in propylene carbonate-toluence (3∶2, v/v) was demonstrated by cyclic voltammetry. The process affords C60H2 as the product. The reaction found is the typical redox-induced process. Translated fromIzvestiya Akodemii Nauk. Seriya Khimicheskaya, No. 6, pp. 1136–1139, June, 1998.  相似文献   

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