Synthesis of C60 end‐capped polymers from azide functional polystyrene via atom transfer radical polymerization

Atom transfer radical polymerization (ATRP) was performed to prepare azide end‐functional polystyrene (PSt‐N₃) with predesigned molecular weight and narrow polydispersity. Then C₆₀ end‐capped polystyrene was synthesized by reacting C₆₀ with PSt‐N₃. The UV‐VIS, DSC, GPC characterizations indicated that C₆₀ was chemically bonded to the end of polystyrene chain, and the brown powder products, which can be dissolved in THF, CHCl₃, DMF, and so forth, were monoadditional and diadditional according to C₆₀. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4519–4523, 2000     

Novel C60‐Anchored Two‐Armed Poly(tert‐butyl acrylate): Synthesis and Characterization

Summary: A multistep synthetic procedure for preparing novel C₆₀‐anchored two‐armed poly(tert‐butyl acrylate) was developed. First, two‐armed poly(tert‐butyl acrylate) bearing a malonate ester core with well‐controlled molecular weight was synthesized through atom transfer radical polymerization. The effective Bingel reaction between C₆₀ and the well‐defined polymer was then carried out to yield C₆₀‐anchored polymer. GPC, ¹H NMR, and UV‐vis spectroscopy indicated that the C₆₀‐anchored polymer was a monosubstituted and ‘closed’ 6,6‐ring‐bridged methanofullerene derivative.

Schematic of a novel C₆₀‐anchored two‐armed polymer.     

Donor–acceptor rod–coil block copolymers comprising poly[2,7‐(9,9‐dihexylfluorene)‐alt‐bithiophene] and fullerene as compatibilizers for organic photovoltaic devices

The successful synthesis is described for a donor–acceptor rod–coil block copolymer comprising blocks of poly[2,7‐(9,9‐dihexylfluorene)‐alt‐bithiophene] (F6T2) and polystyrene functionalized with fullerene (PS(C₆₀)) (F6T2‐b‐PS(C₆₀)). This new material was obtained by combining Suzuki polycondensation with radical addition fragmentation chain transfer. The block copolymer was characterized by nuclear magnetic resonance, gel permeation chromatography, and optical spectroscopy methods. Photophysical data for (F6T2‐b‐PS(C₆₀)) and a related block copolymer (F6T2‐b‐PS(PCBM)) (PCBM, phenyl‐C61‐butyric acid methyl ester) are reported and their performance as compatibilizers in bulk heterojunction organic solar cells is assessed. It is demonstrated that the addition of the rod–coil block copolymers to the active layer extends the operational stability of organic photovoltaic devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 888–903     

Thermal stability of a star‐shaped poly(1,3‐cyclohexadiene)

A star‐shaped poly(1,3‐cyclohexadiene) (PCHD) with a fullerene‐C₆₀ (C₆₀) core (C₆₀‐PCHD) was prepared to examine the thermal stability of the covalent bond between the C₆₀ and PCHD arm in the C₆₀‐PCHD. The covalent bond between the C₆₀ and PCHD arm formed by a 1,2‐cyclohexadiene (CHD) unit on the C₆₀ was stronger than that formed by a 1,4‐CHD unit. The double bond in the CHD unit adjoining the C₆₀ core was a key structure for the stability of that covalent bond. The hydrogenated C₆₀‐PCHD, which did not contain a double bond, possessed significantly higher thermal stability compared to C₆₀‐PCHD. The mechanism of elimination of PCHD arm molecules from the C₆₀ core was thought to proceed via a 1,5‐sigmatropic H‐shift. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2132–2142, 2009     

Thermal stability of the fullerene‐chain link in 6‐arm PS stars with a C60 core

The thermal stability of well‐defined hexa‐adducts (PS)₆C₆₀ in solution at temperatures around 100 °C has been studied by multi‐detector Size Exclusion Chromatography. The degradation reaction corresponds to a quantitative release of the polystyrene arms from the fullerene core through thermal cleavage of the PS‐C₆₀ link. From the kinetics of formation of cut arms and the progressive decrease of the stars' functionality, we could establish that the reaction follows a stepwise “breaking” mechanism where a 6‐arm star is first converted to a 5‐arm star, then to a 4‐arm star, and so on down to the ungrafted arm. Furthermore, not only does the thermal stability of the PS? C₆₀ bond increase if the functionality of the star decreases, but the difference is large enough to allow determination of the kinetics constants for the first three steps. The activation energy for the breaking of an arm‐C₆₀ link is about 65 kJ/mol. The stability of (PS)₆C₆₀ slightly decreases with an increase of the arm length. MALDI‐TOF mass spectroscopy has shown that both C? C bonds in α and β positions to C₆₀ can be cut, but the breaking of the direct fullerene‐arm bond is favored. We have also found that a polyisoprene? C₆₀ bond is about seven times less stable than a PS‐fullerene link upon heating. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4820–4829, 2004     

Solubility characteristics of C60 fullerenes with two well‐defined polystyrene arms in a polystyrene matrix

Four samples of C₆₀‐(PS)₂, i. e., C₆₀ fullerenes with two low‐polydispersity PS arms at the 1,4‐positions, were studied with respect to their solubility and dispersion state in a PS (polystyrene) matrix by the UV spectroscopic method. C₆₀‐bearing polymers were found to be dispersed, in a blend film or a bulk film of itself, either monomolecularly or in aggregates, depending on the chain length of the polymer moiety and blend composition.     

Hydrogen‐bond motifs in N‐monosubstituted derivatives of barbituric acid: 5‐allyl‐5‐isopropyl‐1‐methylbarbituric acid (enallylpropymal) and 1,5‐di(but‐2‐enyl)‐5‐ethylbarbituric acid

Both title structures exhibit essentially planar barbiturate rings. The crystal structure of enallylpropymal (5‐allyl‐5‐isopropyl‐1‐methylbarbituric acid), C₁₁H₁₆N₂O₃, is composed of centrosymmetric N—H...O hydrogen‐bonded dimers, while 1,5‐di(but‐2‐enyl)‐5‐ethylbarbituric acid, C₁₄H₂₀N₂O₃, forms N—H...O hydrogen‐bonded helical chains. Each of the ten known crystal structures of closely related N‐monosubstituted derivatives of barbituric acid displays one of the fundamental N—H...O hydrogen‐bonded motifs of the two title structures, i.e. either a dimer or a chain.     

Photosynthetic Antenna‐Reaction Center Mimicry with a Covalently Linked Monostyryl Boron‐Dipyrromethene–Aza‐Boron‐Dipyrromethene–C60 Triad

An efficient functional mimic of the photosynthetic antenna‐reaction center has been designed and synthesized. The model contains a near‐infrared‐absorbing aza‐boron‐dipyrromethene (ADP) that is connected to a monostyryl boron‐dipyrromethene (BDP) by a click reaction and to a fullerene (C₆₀) using the Prato reaction. The intramolecular photoinduced energy and electron‐transfer processes of this triad as well as the corresponding dyads BDP‐ADP and ADP‐C₆₀ have been studied with steady‐state and time‐resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge‐separated states. Such calculations show that electron transfer from the singlet excited ADP (¹ADP*) to C₆₀ yielding ADP^.+‐C₆₀^.? is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from ¹BDP* to ADP in the dyad BDP‐ADP and electron transfer from ¹ADP* to C₆₀ in the dyad ADP‐C₆₀. Sequential energy and electron transfer have also been clearly observed in the triad BDP‐ADP‐C₆₀. By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈10¹¹ s^?1). The dynamics of electron transfer through ¹ADP* has also been studied by monitoring the formation of C₆₀ radical anion at 1000 nm. A fast charge‐separation process from ¹ADP* to C₆₀ has been detected, which gives the relatively long‐lived BDP‐ADP^.+C₆₀^.? with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge‐separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP‐ADP and ADP‐C₆₀, and the triad BDP‐ADP‐C₆₀ are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems.     

Well‐Organized CdS/C60 in Block Copolymer Micellar Cores

CdS nanoparticles of 4.5 nm diameter were synthesized in poly(2‐vinylpyridine) micellar cores which were obtained by solvating a polystyrene‐block‐poly(2‐vinylpyridine) block copolymer in polystyrene‐selective toluene. Then, a C₆₀‐toluene solution was dispersed into the CdS micelle solution with stirring. This led to the well‐defined organization of two different nanoparticles; specifically: a CdS NP decorated by several/dozens of C₆₀ molecules, because C₆₀ molecules were strongly coordinated with pyridine molecules in the micellar cores by charge‐transfer complexation C–P2VP^δ+. A harmoniously organized CdS/C₆₀ micellar structure was clearly verified by transmission electron microscopy. Fluorescent quenching of CdS nanoparticles, which was strongly affected by neighboring C₆₀ molecules, was observed.

     

4‐Methoxy‐1‐naphthol: chains formed by O—H...O hydrogen bonds and π–π stacking interactions

The structure of 4‐methoxy‐1‐naphthol, C₁₁H₁₀O₂, (I), contains an intermolecular O—H...O hydrogen bond which links the molecules into a simple C(2) chain running parallel to the shortest crystallographic b axis. This chain is reinforced by intermolecular π–π stacking interactions. Comparisons are drawn between the crystal structure of (I) and those of several of its simple analogues, including 1‐naphthol and some monosubstituted derivatives, and that of its isomer 7‐methoxy‐2‐naphthol. This comparison shows a close similarity in the packing of the molecules of its simple analogues that form π‐stacks along the shortest crystallographic axes. A substantial spatial overlap is observed between adjacent molecules in such stacks. In this group of monosubstituted naphthols, the overlap depends mainly on the position of the substituents carried by the naphthalene moiety, and the extent of the overlap depends on the substituent type. By contrast with (I), in the crystal structure of the isomeric 7‐methoxy‐2‐naphthol there are no O—H...O hydrogen bonds or π–π stacking interactions, and sheets are formed by O—H...π and C—H...π interactions.     

Mono‐ and Bis(pyrrolo)tetrathiafulvalene Derivatives Tethered to C60: Synthesis,Photophysical Studies,and Self‐Assembled Monolayers

A series of mono‐ (MPTTF) and bis(pyrrolo)tetrathiafulvalene (BPTTF) derivatives tethered to one or two C₆₀ moieties was synthesized and characterized. The synthetic strategy for these dumbbell‐shaped compounds was based on a 1,3‐dipolar cycloaddition reaction between aldehyde‐functionalized MPTTF/BPTTF derivatives, two different tailor‐made amino acids, and C₆₀. Electronic communication between the MPTTF/BPTTF units and the C₆₀ moieties was studied by a variety of techniques including cyclic voltammetry and absorption spectroscopy. These solution‐based studies indicated no observable electronic communication between the MPTTF/BPTTF units and the C₆₀ moieties. In addition, femtosecond and nanosecond transient absorption spectroscopy revealed, rather surprisingly, that no charge transfer from the MPTTF/BPTTF units to the C₆₀ moieties takes place on excitation of the fullerene moiety. Finally, it was shown that the MPTTF–C₆₀ and C₆₀–BPTTF‐C₆₀ dyad and triad molecules formed self‐assembled monolayers on a Au(111) surface by anchoring to C₆₀.     

Synthesis,Photophysical and Electrochemical Properties of Amide‐Linked Phthalocyanine‐Fullerene Dyad

A new amide‐linked phthalocyanine‐fullerene dyad ZnPc‐C₆₀ was synthesized and characterized. The photophysical and electrochemical properties of the ZnPc‐C₆₀ dyad were investigated. The fluorescence spectrum and quantum yield in different solvents showed the occurrence of photoinduced electron transfer (PET) from the singlet excited ZnPc to C₆₀, which was further confirmed by nanosecond transient absorption spectra and cyclic voltammetry data. The free energy change for charge separation (ΔG_CS) was estimated to be exothermic with ?0.51 eV, which favored the formation of charge‐separation state. The PET from ZnPc to C₆₀ in ZnPc‐C₆₀ made the dyad exhibit stronger reverse saturable absorption performance compared with C₆₀ and the control sample in the Z‐scan experiments, which indicated the synergistic effect of two active moieties in the dyad.     

Photoinduced Electron Transfer between N,N, Nr,N' ‐Tetra‐(p‐methylphenyl)‐4, 4‐diamino‐1, 1'‐diphenyl Ether (TPDAE) and Fullerenes (C60/C70) by Laser Flash Photolysis

The photoinduced electron‐transfer reaction of N, N, N', N'‐tetra‐(p‐methylphenyl)‐4,4'‐diamino‐1,1'‐diphenyl ether (TPDAE) and fullerenes (C₆₀/C₇₀) by nanosecond laser flash photolysis occurred in benzonitrile. Transient absorption spectral measurements were carried out during 532 nm laser flash photolysis of a mixture of the fullerenes (C₆₀/C₇₀) and TPDAE. The electron transfer from the TPDAE to excited triplet state of the fullerenes (C₆₀/C₇₀) quantum yields and rate constants of electron transfer from TPDAE to excited triplet state of fullerenes (C₆₀/C₇₀) in benzonitrile have been evaluated by observing the transient absorption bands in the near‐IR region where the excited triplet state, radical anion of fullerenes (C₆₀/C₇₀) and radical cations of TPDAE are expected to appear.     

Direct Evidence of Significantly Different Chemical Behavior and Excited‐State Dynamics of 1,7‐ and 1,6‐Regioisomers of Pyrrolidinyl‐Substituted Perylene Diimide

Novel bay‐functionalized perylene diimides with additional substitution sites close to the perylene core have been prepared by the reaction between 1,7(6)‐dibromoperylene diimide 6 (dibromo‐PDI) and 2‐(benzyloxymethyl)pyrrolidine 5 . Distinct differences in the chemical behaviors of the 1,7‐ and 1,6‐regioisomers have been discerned. While the 1,6‐dibromo‐PDI produced the corresponding 1,6‐bis‐substituted derivative more efficiently, the 1,7‐dibromo‐PDI underwent predominant mono‐debromination, yielding a mono‐substituted PDI along with a small amount of the corresponding 1,7‐bis‐substituted compound. By varying the reaction conditions, a controlled stepwise bis‐substitution of the bromo substituents was also achieved, allowing the direct synthesis of asymmetrical 1,6‐ and 1,7‐PDIs. The compounds were isolated as individual regioisomers. Fullerene (C₆₀) was then covalently linked at the bay region of the newly prepared PDIs. In this way, two separate sets of perylene diimide–fullerene dyads, namely single‐bridged (SB‐1,7‐PDI‐C₆₀ and SB‐1,6‐PDI‐C₆₀) and double‐bridged (DB‐1,7‐PDI‐C₆₀ and DB‐1,6‐PDI‐C₆₀), were synthesized. The fullerene was intentionally attached at the bay region of the PDI to achieve close proximity of the two chromophores and to ensure an efficient photoinduced electron transfer. A detailed study of the photodynamics has revealed that photoinduced electron transfer from the perylene diimide chromophore to the fullerene occurs in all four dyads in polar benzonitrile, and also occurs in the single‐bridged dyads in nonpolar toluene. The process was found to be substantially faster and more efficient in the dyads containing the 1,7‐regioisomer, both for the singly‐ and double‐bridged molecules. In the case of the single‐bridged dyads, SB‐1,7‐PDI‐C₆₀ and SB‐1,6‐PDI‐C₆₀, different relaxation pathways of their charge‐separated states have been discovered. To the best of our knowledge, this is the first observation of photoinduced electron transfer in PDI‐C₆₀ dyads in a nonpolar medium.     

Hydrogen‐bonding patterns in 3‐alkyl‐3‐hydroxyindolin‐2‐ones

The molecules of racemic 3‐benzoylmethyl‐3‐hydroxyindolin‐2‐one, C₁₆H₁₃NO₃, (I), are linked by a combination of N—H...O and O—H...O hydrogen bonds into a chain of centrosymmetric edge‐fused R₂²(10) and R₄⁴(12) rings. Five monosubstituted analogues of (I), namely racemic 3‐hydroxy‐3‐[(4‐methylbenzoyl)methyl]indolin‐2‐one, C₁₇H₁₅NO₃, (II), racemic 3‐[(4‐fluorobenzoyl)methyl]‐3‐hydroxyindolin‐2‐one, C₁₆H₁₂FNO₃, (III), racemic 3‐[(4‐chlorobenzoyl)methyl]‐3‐hydroxyindolin‐2‐one, C₁₆H₁₂ClNO₃, (IV), racemic 3‐[(4‐bromobenzoyl)methyl]‐3‐hydroxyindolin‐2‐one, C₁₆H₁₂BrNO₃, (V), and racemic 3‐hydroxy‐3‐[(4‐nitrobenzoyl)methyl]indolin‐2‐one, C₁₆H₁₂N₂O₅, (VI), are isomorphous in space group P. In each of compounds (II)–(VI), a combination of N—H...O and O—H...O hydrogen bonds generates a chain of centrosymmetric edge‐fused R₂²(8) and R₂²(10) rings, and these chains are linked into sheets by an aromatic π–π stacking interaction. No two of the structures of (II)–(VI) exhibit the same combination of weak hydrogen bonds of C—H...O and C—H...π(arene) types. The molecules of racemic 3‐hydroxy‐3‐(2‐thienylcarbonylmethyl)indolin‐2‐one, C₁₄H₁₁NO₃S, (VII), form hydrogen‐bonded chains very similar to those in (II)–(VI), but here the sheet formation depends upon a weak π–π stacking interaction between thienyl rings. Comparisons are drawn between the crystal structures of compounds (I)–(VII) and those of some recently reported analogues having no aromatic group in the side chain.     

Well‐Defined Amphiphilic C60‐PEG Conjugates: Water‐Soluble and Thermoresponsive Materials

For the preparation of well‐defined H₂O‐soluble C₆₀ polymers, several C₆₀‐PEG conjugates were prepared from a C₆₀ biscarboxylic acid derivative and monodisperse NH₂‐PEGs (NH₂‐EG_n, n = 4 – 36) via amide conjugation. When the relatively long PEGs (EG_n, n ≥ 12) were employed, the C₆₀‐PEG conjugates became completely H₂O‐soluble by forming micelle‐like structure shown by the data of surface tension, DLS, and cryo‐TEM. Interestingly, these H₂O‐soluble C₆₀‐PEG conjugates (C₆₀(EG_n)₂, n = 12 – 36) showed reversible thermoresponse to form larger aggregates (ca. 1 μm by DLS) at higher temperatures. The temperature for the aggregation was related to the lengths of PEGs attached to C₆₀; 29 °C (C₆₀(EG_n)₂, n = 12), 51 °C (n = 20), and 72 °C (n = 36). This thermoresponse was speculated to occur by dehydration of well‐organized PEG chains in the micelle‐type structure of monodisperse C₆₀‐PEG caused by gauche‐to‐anti conformational change of PEG anchors. This thermoresponse of well‐defined amphiphilic C₆₀‐PEG conjugates indicates potential applications in areas such as temperature sensors and thermoresponsive materials.     

Quantum chemical modeling of the addition reactions of 1‐n‐phenylpropyl radicals to C60 fullerene

Modeling of the addition of various radicals to C₆₀ fullerene is currently an active research area. However, the radicals considered are not able to adequately model polymeric radicals. In this work, we have performed a theoretical study of the possible reactions of C₆₀ fullerene with 1‐n‐phenylpropyl radicals, which are used to model polystyrene radicals. Several possible ways of subsequent addition of up to four 1‐phenylpropyl radicals to C₆₀ have been analyzed, the structures of the intermediates have been defined and thermal properties, such as the activation enthalpies of the corresponding reactions, have been calculated using density functional theory with the approximation of PBE/3z. It is shown that the topology of the spin density distribution on the fullerenyl radical causes regioselectivity for further radical addition. According to the energetic characteristics of the reactions, we assume the possibility of formation of products of one‐, two‐, three‐, and four‐ addition of the growth radical to the fullerene core in radical polymerization of styrene in the presence of C₆₀ fullerene. © 2016 Wiley Periodicals, Inc.     

Advantages and Potential of Lipid‐Membrane‐Incorporating Fullerenes Prepared by the Fullerene‐Exchange Method

Lipid‐membrane‐incorporating C₆₀ and C₇₀ (LMIC₆₀ and LMIC₇₀) were prepared by the fullerene‐exchange reaction from the γ‐cyclodextrin cavity to vesicles (we call this method the “exchange method”). An advantage of this method is that the ratios of [C₆₀]/[lipids] and [C₇₀]/[lipids] can be arbitrarily controlled by adjusting the ratios of the fullerenes and liposome. The maximum ratio (30 mol %) obtained was approximately 14 and 100 times higher than those achieved for LMIC₆₀ and LMIC₇₀, respectively, that were prepared by the classical method, which we call the “premixing method” (dissolving lipids and C₆₀ or C₇₀ in chloroform, followed by concentration and extraction with water). Furthermore, the stabilities and photodynamic activities of the LMIC₆₀ and LMIC₇₀ solutions prepared by the exchange method were shown to be much higher than those prepared by the premixing method. That is, the exchange method was found to be superior to the premixing method as a preparative method of LMIC₆₀ and LMIC₇₀ for applications in photomedical and photomaterials chemistry.     

Energy‐Funneling‐Based Broadband Visible‐Light‐Absorbing Bodipy–C60 Triads and Tetrads as Dual Functional Heavy‐Atom‐Free Organic Triplet Photosensitizers for Photocatalytic Organic Reactions

C₆₀–bodipy triads and tetrads based on the energy‐funneling effect that show broadband absorption in the visible region have been prepared as novel triplet photosensitizers. The new photosensitizers contain two or three different light‐harvesting antennae associated with different absorption wavelengths, resulting in a broad absorption band (450–650 nm). The panchromatic excitation energy harvested by the bodipy moieties is funneled into a spin converter (C₆₀), thus ensuring intersystem crossing and population of the triplet state. Nanosecond time‐resolved transient absorption and spin density analysis indicated that the T₁ state is localized on either C₆₀ or the antennae, depending on the T₁ energy levels of the two entities. The antenna‐localized T₁ state shows a longer lifetime (τ_T=132.9 μs) than the C₆₀‐localized T₁ state (ca. 27.4 μs). We found that the C₆₀ triads and tetrads can be used as dual functional photocatalysts, that is, singlet oxygen (¹O₂) and superoxide radical anion (O₂ ^{. ?}) photosensitizers. In the photooxidation of naphthol to juglone, the ¹O₂ photosensitizing ability of the C₆₀ triad is a factor of 8.9 greater than the conventional triplet photosensitizers tetraphenylporphyrin and methylene blue. The C₆₀ dyads and triads were also used as photocatalysts for O₂ ^{. ?}‐mediated aerobic oxidation of aromatic boronic acids to produce phenols. The reaction times were greatly reduced compared with when [Ru(bpy)₃Cl₂] was used as photocatalyst. Our study of triplet photosensitizers has shown that broadband absorption in the visible spectral region and long‐lived triplet excited states can be useful for the design of new heavy‐atom‐free organic triplet photosensitizers and for the application of these triplet photosensitizers in photo‐organocatalysis.     

Transient Absorption Spectral characterization of Electron Transfer between Fullerenes（C60／C70）and N,N,N’，N’—Tetra（p—methylphenyl）—4,4’—diamino—1,1’—diphenyl Sulphide（TPDAS）

In search of new systems with a photoexcited redox pair which exhibits a strong and stable photoinduced absorption band to understand the photophyscial and photochemical properties of electron transfer between fullernes (C60/C70) and organic donor[N,N,N’，N’-tetra(p-methylphenyl)-4,4’-diamino-1,1’-diphenyl sulphide(TPDAS)],we studied characteristic absorption spectra in the near-IR region obtained from 532nm nanosecond laser flash photolysis of a mixture of the fullerenes (C60/C70) and TPDAS in polar solvents.When fullerenes (C60/C70)were photoexcithed,the rise of the radical anion of fullerenes (C60/C70)with the rapid decay of their excited triplet states were observed in benzonitrile.It can be deduced that the electron transfer reaction does take place from TPDAS to excithed triplet state of rullerens(C60/C70).The rate consants(ket)and quantum yiekls(φet) of this process have been also evaluated.