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1.
It is known that silicon fullerenes cannot maintain perfect cage structures like carbon fullerenes. Previous density-functional theory calculations have shown that even with encapsulated species, nearly all endohedral silicon fullerenes exhibit highly puckered cage structures in comparison with their carbon counterparts. In this work, we present theoretical evidences that the tetrahedral fullerene cage Si(28) can be fully stabilized by encapsulating a tetrahedral metallic cluster (Al(4) or Ga(4)). To our knowledge, this is the first predicted endohedral silicon fullerene that can retain perfectly the same cage structure (without puckering) as the carbon fullerene counterpart (T(d)-C(28) fullerene). Density-functional theory calculations also suggest that the two endohedral metallosilicon fullerenes T(d)-M(4)@Si(28) (M=Al and Ga) can be chemically stable because both clusters have a large highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap ( approximately 0.9 eV), strong spherical aromaticity (nucleus-independent chemical shift value of -36 and -44), and large binding and embedding energies. 相似文献
2.
Fullerenes C60 and C70 have high electron affinity ( 2.6 - 2.8 ev ) and readily form anions on electronchemical reduction1, which were famous as electron acceptor in photo-excitation because of symmetrical shape, large size, and properties of its p - electron system2. After observation of molecular ferromagnetism3 in the tetrakis (dimethylamino ) ethylene salt of C60 as well as the occurrence of ultra-fast photoinduced electron transfer within the dimethyl aniline - C60 complex4, prompted us… 相似文献
3.
He Ping ZENG 《中国化学快报》2002,13(12)
Photoinduced electron transfer processes between fullerenes (C60 / C70) and N, N, N′, N′- tetra - ( p-methylphenyl ) - 4, 4′- diamino - 1, 1′- diphenyl ether ( TPDAE ) have been studied by nanosecond laser flash photolysis. 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 appear. 相似文献
4.
He‐Rng Zeng 《中国化学》2002,20(12):1546-1551
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. 相似文献
5.
Deza M Fowler PW Rassat A Rogers KM 《Journal of chemical information and computer sciences》2000,40(3):550-558
If a fullerene is defined as a finite trivalent graph made up solely of pentagons and hexagons, embedding in only four surfaces is possible: the sphere, torus, Klein bottle, and projective (elliptic) plane. The usual spherical fullerenes have 12 pentagons; elliptic fullerenes, 6; and toroidal and Klein-bottle fullerenes, none. Klein-bottle and elliptic fullerenes are the antipodal quotients of centrosymmetric toroidal and spherical fullerenes, respectively. Extensions to infinite systems (plane fullerenes, cylindrical fullerenes, and space fullerenes) are indicated. Eigenvalue spectra of all four classes of finite fullerenes, are reviewed. Leapfrog fullerenes have equal numbers of positive and negative eigenvalues, with 0, 0, 2, or 4 eigenvalues zero for spherical, elliptic, Klein-bottle, and toroidal cases, respectively. 相似文献
6.
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. 相似文献
7.
Prof. Dr. Yutaka Matsuo Hiromi Oyama Dr. Iwao Soga Dr. Toshihiro Okamoto Dr. Hideyuki Tanaka Dr. Akinori Saeki Prof. Dr. Shu Seki Prof. Dr. Eiichi Nakamura 《化学:亚洲杂志》2013,8(1):121-128
The efficient nucleophilic addition of aryl Grignard reagents (aryl=4‐MeOC6H4, 4‐Me2NC6H4, Ph, 4‐CF3C6H4, and thienyl) to C60 in the presence of DMSO produced 1,2‐arylhydro[60]fullerenes after acid treatment. The reactions of the anions of these arylhydro[60]fullerenes with either dimethylphenylsilylmethyl iodide or dimethyl(2‐isopropoxyphenyl)silylmethyl iodide yielded the target compounds, 1‐aryl‐4‐silylmethyl[60]fullerenes. The properties and structures of these 1‐aryl‐4‐silylmethyl[60]fullerenes (aryl=4‐MeOC6H4, thienyl) were examined by electrochemical studies, X‐ray crystallography, flash‐photolysis time‐resolved microwave‐conductivity (FP‐TRMC) measurements, and electron‐mobility measurements by using a space‐charge‐limited current (SCLC) model. Organic photovoltaic devices with a polymer‐based bulk heterojunction structure and small‐molecule‐based p–n and p–i–n heterojunction configurations were fabricated by using 1‐aryl‐4‐silylmethyl[60]fullerenes as an electron acceptor. The most efficient device exhibited a power‐conversion efficiency of 3.4 % (short‐circuit current density: 8.1 mA/ cm2, open‐circuit voltage: 0.69 V, fill factor: 0.59). 相似文献
8.
Whitener KE 《The journal of physical chemistry. A》2010,114(45):12075-12082
Molecules trapped inside fullerenes exhibit interesting quantum behavior, including quantization of their translational degrees of freedom. In this study, a theoretical framework for predicting quantum properties of nonlinear small molecules in nonsymmetric open-cage fullerenes (OCFs) has been described along the lines of similar theories which treat small molecules inside C(60) and clathrate cages. As an example, the coupled translational-rotational energy structure has been calculated for the case of CH(4) inside a known OCF. The calculated energy levels have been used to calculate the equilibrium fraction of incorporated CH(4) as well as the translational heat capacity for the encapsulated molecule. The heat capacity shows an anomalous maximum at 239 K for CH(4) and 215 K for CD(4) which are not present in free methane. 相似文献
9.
The aggregation behavior of C60 fullerenes and C60 fullerenes with six symmetrically tethered poly(ethylene oxide) oligomers [(PEO)-6-C60] in aqueous solutions has been studied using implicit solvent molecular dynamics simulations. Our simulations reveal that while the attraction between two (PEO)-6-C60 fullerenes in aqueous solution is stronger and longer range than that between two bare C60 fullerenes, the (PEO)-6-C60 fullerenes do not phase-separate in water but rather aggregate in chain-like clusters at concentrations where unmodified fullerenes completely phase-separate. 相似文献
10.
This paper is a tutorial review of the host-guest chemistry of fullerenes and metalloporphyrin. Among various host molecules for fullerenes, cyclic hosts composed of metalloporphyrin moieties possess one of the highest affinities toward fullerenes, which can be widely tuned simply by changing the central metal ions of the porphyrin moieties. Inclusion of fullerenes occurs not only by van der Waals interactions but also, in some cases, via pi-electronic charge-transfer from the host metalloporphyrin moieties to the guest fullerenes. Fullerenes such as C(120), upon inclusion with cyclic metalloporphyrin dimers, show an oscillatory motion within the host cavity, whose frequency reflects the solvation/desolvation dynamics of the fullerenes. A molecularly engineered metalloporphyrin host with a self-assembling capability allows a guest-directed formation of a supramolecular peapod, where included fullerenes, as peas, are aligned along the self-assembled metalloporphyrin nanotube, as a pod. Furthermore, certain metalloporphyrin hosts are applicable to the selective extraction of low-abundance higher fullerenes from an industrial production source and also allow spectroscopic discrimination of chiral fullerenes. 相似文献
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13.
N. I. Alekseev N. A. Charykov 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2012,86(2):268-276
A joint analysis of fullerene assembly kinetics and gas flow dynamics in an arc chamber for the production of fullerenes showed
that the effective annealing of fullerenes and the evident dominance of “magic” fullerenes C60 and C70 were mainly explained by the difference between the thermal dissociation rates of these and less stable C62 and C68 fullerenes. The percent of “nonmagic” fullerenes was also shown to depend on the structure of the gas flows formed in the
arc discharge chamber. The majority of newly formed fullerenes were not immediately removed from the chamber, bur were trapped
by closed gas flows. Back in the hot region of the chamber, fullerenes were simultaneously annealed and dissociated under
the action of high temperature and, partially, UV radiation. The “nonmagic” fullerenes were most actively suppressed in a
non-pumpable discharge chamber. 相似文献
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16.
V. I. Sokolov 《Russian Journal of Coordination Chemistry》2007,33(10):711-724
Fullerenes are considered as ligands in transition metal π-complexes. The following aspects are discussed: metals able to form complexes with fullerenes; haptic numbers; homo-and heteroligand complexes; ligand compatibility with fullerenes for different metals, including fullerenes with a disturbed structure of conjugation. 相似文献
17.
We calculated the partitioning of pi-electrons within individual pentagonal and hexagonal rings of fullerenes for a collection of fullerenes from C20 to C72 by constructing their Kekulé valence structures and averaging the pi-electron content of individual rings over all Kekulé valence structures. The resulting information is collected in Table 2, which when combined with the Schlegel diagram of fullerenes (illustrated in Figure 7) uniquely characterizes each of the 19 fullerenes considered. The results are interpreted as the basic information on the distributions (variation) of the local (ring) pi-electron density. 相似文献
18.
Molecular-dynamics simulations of a single C(60) fullerene and pairs of C(60) fullerenes in aqueous solution have been performed for the purpose of obtaining improved understanding of the nature of solvent-induced interactions between C(60) fullerenes in water. Our simulations reveal repulsive solvent-induced interactions between two C(60) fullerenes in aqueous solution in contrast to the associative effects observed for conventional nonpolar solutes. A decomposition of the solvent-induced potential of mean force between fullerenes into entropy and energy (enthalpy) contributions reveals that the water-induced repulsion between fullerenes is energetic in origin, contrasting strongly to entropy-driven association observed for conventional nonpolar solutes. The dominance of energy in the solvent-induced interactions between C(60) fullerenes arises primarily from the high atomic density of the C(60) molecule, resulting in strong C(60)-water van der Waals attraction that is reduced upon association of the fullerenes. The water-induced repulsion is found to decrease with increasing temperature due largely to an increasing contribution from a relatively weak entropy-driven association. 相似文献
19.
Bhattacharya S Nayak SK Chattopadhyay S Banerjee M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,63(1):200-206
Supramolecular interactions of 24,26-dimethoxy-25,27-dihydroxy calix[4]arene (1) with [60]- and [70]fullerenes have been studied in only chloroform and in a ternary solvent mixture comprising of chloroform, ethyl alcohol and toluene by UV-vis absorption spectrophotometric method. The experimental results are explained using the model that takes into account the interaction between electronic subsystems of 1 and fullerene. The most interesting feature is the preference of [60]fullerene over [70]fullerene for 1 in ternary solvent mixture as revealed by higher value of formation constant of [60]fullerene/1 complex. The selectivity towards [60]fullerene opens up the way toward self-assembling systems and new separation and purification methods for fullerenes. 相似文献