Synthesis of a novel [60]fullerene pearl-necklace polymer,poly(4,4′-carbonylbisphenylene trans-2-[60]fullerenobisacetamide)

A novel [60]fullerene pearl-necklace polymer, poly(4,4′-carbonylbisphenylene trans-2-[60]fullerenobisacetamide), was synthesized by a direct polycondensation of trans-2-[60]fullerenobisacetic acid with 4,4′-diaminobenzophenone in the presence of large excesses of triphenyl phosphite and pyridine. In the present polymer, [60]fullerene pearls and diamine linkers were attached to each other by methano-carbonyl connectors. The molecular weight M_w of the polymer was determined to be 4.5 × 10⁴ on the basis of the TOF-MS, and a GPC analysis of the polymer using polystyrene standards showed a weight-average molecular weight of 5.3 × 10⁴. The UV-vis spectrum of the resultant polymer in N,N-dimethylacetamide (DMAc) exhibited a broad absorption (λ_max 310 nm, ε 2.1 × 10⁴ L · mol⁻¹ · cm⁻¹), tailing to longer wavelengths, and a fluorenscence peak centered at 550 nm was observed in DMAc. There was observed a large downfield-shift of the cyclopropane methyne proton in the ¹H-NMR spectra from 4.57 ppm of the ethyl ester to 5.78 ppm of the polyamide. These observations indicate that the present polyamide is a high-molecular-weight [60]fullerene pearl-necklace polymer and that the cyclopropane rings are efficient to make the [60]fullerene cages and the diamine components conjugatable. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3632–3637, 1999     

[60]富勒烯[2＋2]环加成反应的研究进展

[2＋2]环加成反应是对C₆₀进行化学修饰的重要反应之一, 重点从[2＋2]环加成的典型反应、主要试剂及反应机理等方面进行了综述.     

Synthesis and stability of linear and star polymers containing [C60] fullerene

Linear and symmetric star block copolymers of styrene and isoprene containing [C₆₀] fullerene were synthesized by anionic polymerization and appropriate linking postpolymerization chemistry. In all block copolymers, the C₆₀ was connected to the terminal polyisoprene (PI) block. The composition of the copolymers was kept constant (～30% wt PI), whereas the molecular weight of the diblock chains was varied. The polymers were characterized with a number of techniques, including size exclusion chromatography, membrane osmometry, and ¹H NMR spectroscopy. The combined characterization results showed that the synthetic procedures followed led to well‐defined materials. However, degradation of the fractionated star‐shaped copolymers was observed after storage for 2 months at 4 °C, whereas the nonfractionated material was stable. To further elucidate the reasons for this degradation, we prepared and studied a four‐arm star copolymer with the polystyrene part connected to C₆₀ and a six‐arm star homopolymer of styrene. These polymers as well as linear copolymers end‐capped, through ? N<, with C₆₀ were stable. Possible reasons are discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2494–2507, 2001     

Study of the factors determining the outcome of cycloaddition of isocyanurato-substituted azides to [60]fullerene

The final outcome of cycloaddition of isocyanuratoalkyl azides to C₆₀ depends on the temperature, the thermal stability of azides, the substituents in the isocyanurate ring, and the number of methylene groups in the alkyl radical. The thermal transformations of the monoadducts obtained were studied.     

Synthesis of a single isomer of the bis-adduct of isocyanurato-substituted azide with [60]fullerene

A single di(azahomo)[60]fullerene isomer was prepared for the first time by the reaction between [60]fullerene and isocyanurato-substituted azide. The structure of the product was established by ¹H and ¹³C NMR, UV, and IR spectroscopy.     

Reactions of [60]fullerene with 2-azidopyrimidines

The reaction of [60]fullerene with 2-azidopyrimidines affords fullerenoimidazopyrimidines, whose electron affinity is higher than that of nonmodified C₆₀.     

Formation and Optical Absorption of Clusters of the p-tert-butylcalix[8]arene:C60 Complex

Depending on the initial concentrations of fullerene (C₆₀) and p-tert-butyl calix[8]arene (C[8]A) in toluene, two regimes of their interaction were distinguished. The changes in optical absorption of C₆₀:C[8]A mixed solutions observed over a period of time suggest that the following consecutive processes take place upon interaction between C₆₀ and C[8]A in toluene: (1) molecular inclusion, and (2) growth and sedimentation of the insoluble C₆₀/C[8]A clusters. At increased concentrations of the components, process (2) is suppressed and stable C₆₀/C[8]A colloids can be formed. Spectral features of these colloids in different solvents clearly indicate the difference between self-aggregated C₆₀ and small clusters of the complex. A specific influence of the C[8]A cage on the entrapped C₆₀ molecules is also confirmed by IR spectroscopy of the complex in the solid state.     

Energy level tunable pre-click functionalization of [60]fullerene for nonlinear optics

[2+2] click chemistry followed by Prato reaction is reported the first time for energy level tunable functionalization of C₆₀. The novel kind of D–A–A C₆₀ charge-transfer complexes exhibits strikingly enhanced optoelectronic properties and significant third-order nonlinear optical potentials. Meanwhile, structures of the ‘click’ C₆₀ products were fully characterized by NMR, IR, and MS. By introducing TCNE, TCNQ, F₄-TCNQ click monomers, we obtained energy level tunable fullerene derivatives in high solubility, which was beneficial for processing. Furthermore, UV–vis spectra were enlarged with end-absorptions into the near infrared region, indicating excellent nonlinear optical properties. The electrochemical properties have been studied by cyclic voltammograms, which were in good correlation with the optical spectroscopic and DFT data.     

Study on the Inclusion Complex of C_(60) and Calix[8]arene Tetraphenyl Ether

Fullerenehasgeneratedarapidlygrowingandactiveresearchareal.InclusioncomplexesoffullerenehavebeenpreparedforCoowithavarietyofhostsystemsincludingcalixarenes,cyclotriveratrylene,andy-cyclodextrin.TheselectiveformationofaclathratefromCooandcall-c[8]areneswasexcellentlyutilizedfortheseparationofCooandC,,'.HereinwereportthatCoocanbeincludedinthecavityofanewkindoffunctionnedcalixlslarene,p-tert-butylcall-c[8]arenetetraphenylether(1).ThefixtureofCooand1(lfZmolarratio)wasrefluxedintoluenefor2--3h,d…     

Synthesis and properties of polyamides with [60]fullerene in the main chain

A novel series of polyamides having [60]fullerene moieties in the main chain were synthesized by a direct polycondensation of [60]fullerenobis(acetic acid) or [60]fullerenobis(acetic acid)/isophthalic acid mixture with a diamine in the presence of triphenyl phosphite and pyridine. Various properties of the polyamides were characterized by means of IR, GPC, TGA, DSC, UV–visible, and photoluminescence. The molecular weight M_w of the [60]fullerene-containing polyamides was observed in the range from about 300,000 to 3,000; upon the changing of the ratio of [60]fullerenobis(acetic acid)/isophthalic acid in the starting mixture, the resulting M_w decreased with increasing the ratio. Most of the thermal and optical properties gradually changed as the ratio changed; the major optical absorption band in visible range exhibited a significant tailing, which shifted toward a longer wavelength, while the photoluminescence spectrum red-shifted with increasing [60]fullerene content. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3139–3146, 1998     

Unexpected reactions of [60]fullerene involving tertiary amines and insight into the reaction mechanisms

Thermal reactions of [60]fullerene with amino acid ester hydrochlorides and triethylamine in o-dichlorobenzene at reflux afforded pyrrolidinofullerene derivatives containing the CH(3)CH moiety and originating from triethylamine through an unusual C-N bond cleavage. Detailed investigation of these thermal reactions resulted in the discovery of unprecedented reactions between C(60) and tertiary amines and of reactions of C(60) with tertiary amines and aldehydes, giving cyclopentafullerene derivatives with high stereoselectivity. Plausible reaction mechanisms for the product formation involving the uncommon C-N bond cleavage of tertiary amines were proposed on the basis of extensive experimental results.     

Addition of diphenylphosphinoyl azide to [60]fullerene

The reaction of [60]fullerene with diphenylphosphinoyl azide in toluene or ino-dichlorobenzene in the presence of traces of water affords 2-[N-(diphenylphosphoryl)amino]-1-hydroxy[60]fullerene This reaction in THF gives a mixture of (N-diphenylphosphoryl)[60]fullerenol[1,2-b]aziridine and a product of partial hydrolysis of the bisadduct of phosphorylated azide and fullerene. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2168–2172, November, 1999.     

Synthesis of Starburst Oligoanilino[60]fullerene and Poly(Dimethylsiloxane) Triblock Copolymers

Abstract

A new synthetic approach for the fabrication of core‐shell like conducting elastomers was described. The approach utilized the facile intermolecular self‐assembly of poly(dimethylsiloxane) (PDMS) in DMSO leading to formation of a core particle, while soluble oligoaniline (A _x ) segments dispersed in the solution phase resembling a shell overlayer for building the morphology. This morphology was demonstrated by bis[penta(tetraanilinofullereno)] bis(aminopropyl)poly(dimethylsiloxane) [PDMS‐(F5A₄)₂] triblock co‐oligomers synthesized using a functionalized C₆₀ derivative as a linker. Observation of ¹H NMR spectroscopic responses on the PDMS particle formation in DMSO‐d ₆ is consistent with the proposed core‐shell geometry with oligoaniline moieties located at the shell overlayer.     

Photophysical Properties and Photoinduced Electron Transfer between[60]Fullerene—containing Cyclic Sulphoxide [C60—C60H8SO]and Tetrathiafulvalene（TTF） by Laser Flash Photolysis

Photoinduced electron transfer(PET) processes between C60-C6H8SO and Tetrathiafulvalene(TTF) have been studied by nanosecond laser photolysis.Quantrm yiekds(φet) and rate constants of electron transfer(ket) from TTF to excited triplet state of[60] fullerene-containing cyclic sulphoxide in benzonitrile(BN) have been evaluated by observing the transient absorption bands in the NIR region.With the decay of excited triplet state of [60]fullerene-containing cyclic suplhoxide,the rise of radical anion of [60]fullerene-containing cyclic sulphoxinde is observed.     

单加成环丙烷富勒烯膦酸酯衍生物的合成与电化学性能

在Mn(OAc)₃•2H₂O催化下, C₆₀分别和亚甲基二膦酸四乙酯、氰基亚甲基膦酸二乙酯或乙氧羰基亚甲基膦酸二乙酯在氯苯中回流, 生成3个单加成环丙烷富勒烯膦酸衍生物C₆₀C(R)PO(OEt)₂ [1, R＝PO(OEt)₂; 2, R＝COOEt; 3, R＝CN]. 与以前报道的Bingel反应法相比, 该方法副产物少并且缩短了反应时间. 采用循环伏安法发现1, 2的还原电位相对于C₆₀发生负移, 而3的还原电位相对于C₆₀却正移40 mV, 表明引入象氰基一样具有很强吸电子能力的取代基团, 可以改善富勒烯球的电化学性能, 合成电子接受能力较强的富勒烯衍生物.     

C_(60)吡咯烷聚硅氧烷的合成及其在毛细管气相色谱中的应用

通过Ｃ６０吡咯烷衍生物（Ⅰ）和甲基二氯硅烷的硅氢加成产物和端羟基甲基硅油缩合,合成了首例Ｃ６０衍生物气相色谱固定相——Ｃ６０吡咯烷聚硅氧烷（Ⅱ）,并首次研究了它在毛细管气相色谱中的应用。结果表明,该固定相可有效分离多环芳烃,对高沸点的邻苯二甲酸二酯类化合物有很好的分离效果,且有很好的热稳定性,３６０℃时基线漂移量为５ｆＡ。     

Anionic copolymerization of [60]fullerene with styrene initiated by sodium naphthalene

The novel C₆₀–styrene copolymers with different C₆₀ contents were prepared in sodium naphthalene-initiated anionic polymerization reactions. Like the pure polystyrene, these copolymers exhibited the high solvency in many common organic solvents, even for the copolymer with high C₆₀ content. In the polymerization process of C₆₀ with styrene an important side reaction, i.e., reaction of C₆₀ with sodium naphthalene, would occur simultaneously, whereas crosslinking reaction may be negligible. ¹³C-NMR results provided an evidence that C₆₀ was incorporated covalently into the polystyrene backbone. In contrast to pure polystyrene, the TGA spectrum of copolymer containing ∼ 13% of C₆₀ shows two plateaus. The polystyrene chain segment in copolymer decomposed first at 300–400°C. Then the fullerene units reptured from the corresponding polystyrene fragments attached directly to the C₆₀ cores at 500–638°C. XRD evidence indicates that the degree of order of polymers increases with the fullerene content increased in terms of crystallography. Incorporation of C₆₀ into polystyrene results in the formation of new crystal gratings or crystallization phases. In addition, it was also found that [60]fullerene and its polyanion salts [C₆₀ⁿ⁻(M⁺)_n, M = Li, Na] cannot be used to initiate the anionic polymerization of some monomers such as acrylonitrile and styrene, etc.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2653–2663, 1998     

Ferric perchlorate-mediated radical reactions of [60]fullerene

Transition-metal-salt-mediated radical reactions of fullerenes have attracted extensive attention as a new and important method for fullerene functionalization. The application of relatively cheap and easily available ferric perchlorate (Fe(ClO 4 ) 3 ) to the synthesis of [60]fullerene (C 60 ) has demonstrated remarkable advantages and afforded a series of novel fullerene derivatives. In this review we present our recent progress in this area and summarize the reactions of C 60 with malonate esters, β-keto esters, nitriles, aldehydes/ketones, and arylboronic acids in the presence of Fe(ClO 4 ) 3 to afford the C 60-fused disubstituted lactones, C 60-fused hemiketal, C 60-fused dihydrofuran, C 60-fused oxazoles, C 60-fused 1,3-dioxolanes, and fullerenyl boronic esters. The possible reaction mechanisms for the above-mentioned reactions are also described in detail.     

Exploring the photoinduced electron transfer reactivity of aza[60]fullerene iminium cation

Photolysis of (C₅₉N)₂ solutions in the presence of neutral π-donors, such as arenes and electron-rich alkenes leads to a series of novel aza[60]fullerene monoadducts. The key step of the reaction involves a photoinduced electron transfer from the donor molecule to the iminium cation of aza[60]fullerene, followed by radical coupling of the resulting aza[60]fullerenyl radical with an intermediate stabilized radical derived from the substrate. This type of reactivity has been proven efficient with arenes having oxidation potential higher than about 1.5 V. Simple olefins, such as tri- and tetra-methylethylene, as well as cyclohexene, can also participate in this kind of photoinduced electron transfer-initiated reaction with C₅₉N⁺, affording the corresponding aza[60]fullerene derivatives. In the case of 2-methoxyprop-1-ene, 2,4-hexadiene, and β,β-dimethylstyrene, [2+2] cycloaddition reactions with the aza[60]fullerene carbon shell dominate, leading to a mixture of unidentified multiadducts.     

富勒烯[60]膦酸酯衍生物纳米颗粒水悬液的制备与自由基清除活性

自由基清除是富勒烯及其衍生物的一种重要特性. 首次制备了1种二加成亚甲基富勒烯[60]膦酸酯衍生物(bis-methanophosphonate [60]fullerene, BMPF)的纳米颗粒水悬液(n-BMPF), 并采用邻苯三酚自氧化法结合分光光度法, 测定了n-BMPF对超氧阴离子自由基的清除作用. 结果显示, 制备的n-BMPF溶液较稳定, 适合生物学实验. 同时, 它表现出很强的清除超氧阴离子自由基的能力, 并具有浓度依赖性. 当n-BMPF的终浓度为12 μmol/L时, 其对超氧阴离子自由基的清除率达到91.96%. n-BMPF的活性远大于已报道具有自由基清除作用的水溶性富勒烯衍生物富勒醇. 这些数据表明n-BMPF可能作为一种新型高效的自由基清除剂, 在生物医学领域具有潜在的应用价值.