Photophysical properties of closely-coupled, binuclear ruthenium(II) bis(2,2':6',2''-terpyridine) complexes

The photophysical properties of closely-coupled, binuclear complexes formed by connecting two ruthenium(II) bis(2,2':6',2'-terpyridine) complexes via an alkynylene group are compared to those of the parent complex. The dimers exhibit red-shifted emission maxima and prolonged triplet lifetimes in deoxygenated solution. Triplet quantum yields are much less than unity and the dimers generate singlet molecular oxygen with low quantum efficiency. Temperature dependence emission studies indicate coupling to higher-energy triplet states while cyclic voltammetry shows that the metal centres are only very weakly coupled but that extensive electron delocalization occurs upon one-electron reduction. The radiative rate constants derived for these dimers are relatively low, because the lowest-energy metal-to-ligand, charge-transfer states possess increased triplet character. In contrast, the rate constants for nonradiative decay of the lowest-energy triplet states are kept low by extended electron delocalization over the polytopic ligand. The poor triplet yields are a consequence of partitioning at the second triplet level.     

Intramolecular energy-transfer processes in a bis(porphyrin)-ruthenium(II) bis(2,2':6',2'-terpyridine) molecular array

A molecular triad has been synthesized comprising two free-base porphyrin terminals linked to a central ruthenium(II) bis(2,2':6',2'-terpyridine) subunit via meso-phenylene groups. Illumination into the ruthenium(II) complex is accompanied by rapid intramolecular energy transfer from the metal-to-ligand, charge-transfer (MLCT) triplet to the lowest-energy pi-pi* triplet state localized on one of the porphyrin subunits. Transfer takes place from a vibrationally excited level which lowers the activation energy. The electronic coupling matrix element for this process is 73 cm(-1). Selective illumination into the lowest-energy singlet excited state (S1) localized on the porphyrin leads to fast singlet-triplet energy transfer that populates the MLCT triplet state with high efficiency. This latter process occurs via Dexter-type electron exchange at room temperature, but the activation energy is high and the reaction is prohibited at low temperature. For this latter process, the electronic coupling matrix element is only 8 cm(-1).     

Photo-induced transformations in 2,2':5',2'-terthiophene thin films on silver

We report on transient photo-induced structural changes of 2,2':5',2'-terthiophene (3T) adsorbed on silver nanoparticles. Surface-enhanced Raman scattering (SERS) data show that the film thickness predetermines the eventual course of these changes. In particular, for high molecular concentrations (thick adsorbate layers), illumination leads to a photoinduced polymerization of the 3T film. For thin layers ( approximately monolayer coverage), the photoinduced spectral evolution is qualitatively different. We interpret the latter process as a cleavage of the terthiophene molecule, resulting in isolated thiophene units. Calculations of excitation energies for 3T + 3Ag+ and 1T + Ag+ revealed visible transitions, while calculated Raman frequencies indicated 1T as a possible photoproduct. As no photoinduced transformations are observed for 3T in the solid or solution phases, it is likely that the processes reported here originate in surface-enhanced charge-transfer between the Ag-surface and the organic adsorbate.     

Solid-state synthesis of poly(3',4'-dimethoxy-2,2':5',2"- terthiophene): comparison with poly(terthiophene) and poly(3',4'-ethylenedioxy-2,2':5',2"- terthiophene)

A new terthiophene monomer: 3',4'-dimethoxy-2,2':5',2"-terthiophene (TMT) was synthesized and characterized by 1H-NMR, 13C-NMR and FTIR. The solid-state oxidative polymerizations of TMT were performed in various ratios of oxidant (FeCl?) to monomer (TMT). The resulting polymers were characterized by 1H-NMR, FTIR, UV-vis-NIR, GPC, X-ray diffraction, CV, as well as TGA and conductivity measurements. The structure and properties of poly (TMT) were compared with those of polyterthiophene [poly(TT)] and poly (3',4'-ethylenedioxy-2,2':5',2"-terthiophene) [poly(TET)] prepared under the same polymerization conditions. After comparative analysis with poly(TT) and poly(TET), the effects of the dimethoxy substituent and FeCl? on the structural and physicochemical properties of the poly(TMT)s were discussed in depth. The comparison suggested that the dimethoxy-substituted polymer did not display higher crystallinity, thermal stability, conductivity and electrochemical activity than ethylenedioxy substituted one. The results also showed that the effect of FeCl? on poly(TMT) was similar that seen with the poly(TT), in which the oxidation degree, electrochemical activity and conductivity increased steadily with increasing [FeCl?/[TT] ratio. Furthermore, the poly(TMT) and poly(TT) are mostly made up of dimers with a small amount of higher molecular weight components.     

4'-(5'-R-pyrimidyl)-2,2':6',2'-terpyridyl (R = H, OEt, Ph, Cl, CN) platinum(II) phenylacetylide complexes: synthesis and photophysics

A series of new square-planar 4'-(5'-R-pyrimidyl)-2,2':6',2'-terpyridyl platinum(II) phenylacetylide complexes ( 1a- 5a) bearing different substituents (R = H, OEt, Ph, Cl, CN) on the pyrimidyl ring have been synthesized and characterized. The electronic absorption, photoluminescence, and triplet transient difference absorption spectra were investigated. All of the complexes exhibit broad, moderately strong absorption between 400 and 500 nm that can be tentatively assigned to the metal-to-ligand charge transfer ( (1)MLCT) transition, possibly mixed with some ligand-to-ligand charge transfer ( (1)LLCT) character. Photoluminescence arising from the (3)MLCT state was observed both in fluid solutions at room temperature and in a rigid matrix at 77 K. The (1)MLCT/ (1)LLCT absorption bands and the (3)MLCT emission bands for 1a- 5a red-shift in comparison to those of the corresponding 4'-toly-2,2':6',2'-terpyridyl platinum(II) phenylacetylide complex. In addition, the energies of the (1)MLCT/ (1)LLCT absorption and the (3)MLCT emission bands exhibit a linear correlation with the Hammett constant (sigma p) of the 5'-substituent on the pyrimidyl ring. The lifetime of the (3)MLCT emission at room temperature is governed by the energy gap law. The triplet transient difference absorption spectra of 1a- 5a exhibit a broad absorption band from 500 to 800 nm, and a bleaching band between 420 and 500 nm. Complex 5a, which contains the -CN substituent, exhibits a lower-energy triplet absorption band at 785 nm and a shorter lifetime (130 ns) in CH 3CN than 2a, which has the -OEt substituent, does (lambda T1-Tn (max) = 720 nm, tau T = 660 ns). The triplet excited-state absorption coefficients at the band maxima for 1a- 5a vary from 36 600 L.mol (-1).cm (-1) to 115 090 L.mol (-1).cm (-1), and the quantum yields of the triplet excited-state formation range from 0.19 to 0.66. All complexes exhibit a moderate nonlinear transmission for nanosecond laser pulses at 532 nm. Moreover, these complexes can generate singlet oxygen efficiently in air-saturated CH 3CN solutions, with the singlet oxygen generation quantum yield (Phi Delta) varying from 0.24 to 0.46.     

Comparison of the photophysical properties of osmium(II) bis(2,2':6',2' '-terpyridine) and the corresponding ethynylated derivative

The photophysical properties of osmium(II) bis(2,2':6',2' '-terpyridine) have been recorded over a wide temperature range. An emission band is observed and attributed to radiative decay of the lowest-energy metal-to-ligand, charge-transfer (MLCT) triplet state. This triplet is coupled to two other triplet states that lie at higher energy. The second triplet, believed to be of MLCT character, is reached by crossing a barrier of only 640 cm(-1), but the highest-energy triplet, considered to be of metal-centered (MC) character, is separated from the lowest-energy MLCT triplet by a barrier of 3500 cm(-1). Analysis of the emission spectrum shows that both low- and high-frequency modes are involved in the decay process, while weak emission is seen from the second excited triplet state. The magnitude of the low- and high-frequency modes depends on temperature in fluid solution but not in a KBr disk. Apart from a substantial lowering of the triplet energy, the photophysical properties are relatively insensitive to the presence of an ethynylene substituent at the 4' position of each terpyridine ligand. However, the barrier to reaching the MC triplet is markedly reduced, and the vibrational modes become less sensitive to changes in temperature.     

Reversible luminescence switching in a ruthenium(II) bis(2,2':6',2'-terpyridine)-benzoquinone dyad

An electroactive luminescent switch has been synthesized that comprises a hydroquinone-functionalized 2,2':6',2'-terpyridine ligand coordinated to a ruthenium(II) (4'-phenylethynyl-2,2':6',2'-terpyridine) fragment. The assembly is sufficiently rigid that the hydroquinone-chromophore distance is fixed. Excitation of the complex via the characteristic metal-to-ligand charge-transfer (MLCT) absorption band produces an excited triplet state in which the promoted electron is localized on the terpyridine ligand bearing the acetylenic group. The triplet lifetime in butyronitrile solution at room temperature is 46 +/- 3 ns but increases markedly at lower temperature. Oxidation of the hydroquinone to the corresponding benzoquinone switches on an electron-transfer process whereby the MLCT triplet donates an electron to the quinone. This reaction reduces the triplet lifetime to 190 +/- 12 ps and essentially extinguishes emission. The rate of electron transfer depends on temperature in line with classical Marcus theory, allowing calculation of the electronic coupling matrix element and the reorganization energy as being 22 cm(-1) and 0.84 eV, respectively. The switching behavior can be monitored using luminescence spectroelectrochemistry. The on/off level is set by temperature and increases as the temperature is lowered.     

Photophysical properties of binuclear ruthenium(ii) bis(2,2':6',2''-terpyridine) complexes built around a central 2,2'-bipyrimidine receptor

A binuclear complex has been synthesized having ruthenium(ii) bis(2,2':6',2'-terpyridine) terminals attached to a central 2,2'-bipyrimidine unit via ethynylene groups. Cyclic voltammetry indicates that the substituted terpyridine is the most easily reduced subunit and the main chromophore involves charge transfer from the metal centre to this ligand. The resultant metal-to-ligand, charge-transfer (MLCT) triplet state is weakly emissive and has a lifetime of 60 ns in deoxygenated solution at room temperature. The luminescence yield and lifetime increase with decreasing temperature in a manner that indicates the lowest-energy MLCT triplet couples to at least two higher-energy triplets. Cations can bind to the central bipyrimidine unit, forming both 1:1 and 1:2 (ligand:metal) complexes as confirmed by electrospray MS analysis. The photophysical properties depend on the number of bound cations and on the nature of the cation. In the specific case of binding zinc(ii) cations, the 1:1 complex has a triplet lifetime of 8.0 ns while that of the 1:2 complex is 1.8 ns. The 1:1 complexes formed with Ba(2+) and Mg(2+) are more luminescent than is the parent compound while the 1:2 complexes are much less luminescent. It is shown that the coordinated cations raise the reduction potential of the central bipyrimidine unit and thereby increase the activation energy for coupling with the metal-centred state. Complexation also introduces a non-emissive intramolecular charge-transfer (ICT) state that couples to the lowest-energy MLCT triplet and provides an additional non-radiative decay route. The triplet state of the 1:2 complex formed with added Zn(2+) cations decays preferentially via this ICT state.     

含铁磁耦合Ni3单元的均苯三甲酸桥联双层镍(II)配合物

使用均苯三甲酸与碳酸镍在水热条件下反应得到了一例新的二维双层Ni(II)配位聚合物Ni3(BTC)2(μ-H2O)26H2O。二维层包含syn-syn羧酸桥和水桥连接的三核Ni3单元,进一步用均苯三甲酸上的苯环连接成二维层状结构。磁性研究表明,相邻Ni2+离子间存在弱的铁磁耦合作用。水桥连镍离子的桥联键角为122.8(3)deg,所以通过该水桥镍离子间应该呈现反铁磁耦合。因此,实验结果证明了syn-syn羧酸桥传递铁磁耦合,而且铁磁耦合大于反铁磁作用,最终配合物呈弱的铁磁耦合。基于本工作和文献报道的含syn-syn 羧酸混合桥联镍配合物的磁性,我们总结出下面结论：Ni–O–C–O–Ni的共面性与否决定了配合物的磁性。共面性好的Ni–O–C–O–Ni导致中等强度的反铁磁耦合,而共面性差会消弱反铁磁作用,甚至出现由反铁磁变为铁磁耦合。标题配合物中羧酸桥所传递的铁磁性可能就归因于Ni–O–C–O–Ni的不共平面性。因此,与含羧酸桥的混合桥联双核铜(II)配合物类似,轨道补偿效应(the orbital complementary effect (OCE))对于解释水/羧酸混合桥联镍(II)配合物的磁性也同样适用。     

Temperature-induced switching of the mechanism for intramolecular energy transfer in a 2,2':6',2' '-Terpyridine-based Ru(II)-Os(II) trinuclear array

The synthesis and photophysical properties of a linear 2,2':6',2' '-terpyridine-based trinuclear Ru(II)-Os(II) nanometer-sized array are described. This array comprises two bis(2,2':6',2' '-terpyridine) ruthenium(II) terminals connected via alkoxy-strapped 4,4'-diethynylated biphenylene units to a central bis(2,2':6',2' '-terpyridine) osmium(II) core. The mixed-metal linear array was prepared using the "synthesis at metal" approach, and the Ru(II)-Ru(II) separation is ca. 50 A. Energy transfer occurs with high efficiency from the Ru(II) units to the Os(II) center at all temperatures. Forster-type energy transfer prevails in a glassy matrix at very low temperature, but this is augmented by Dexter-type electron exchange at higher temperatures. This latter process, which is weakly activated, involves long-range superexchange interactions between the metal centers. In fluid solution, a strongly activated process provides for fast energy transfer. Here, a charge-transfer (CT) state localized on the bridge is populated as an intermediate species. The CT triplet does not undergo direct charge recombination to form the ground state but transfers energy, possibly via a second CT state, to the Os(II)-based acceptor. The short tethering strap constrains the geometry of the linker, especially in a glassy matrix, such that low-temperature electron exchange occurs across a particular torsion angle of 37 degrees . The probability of triplet energy transfer depends on temperature but always exceeds 75%.     

Electron delocalization in a ruthenium(II) Bis(2,2':6',2' '-terpyridyl) complex

Photophysical properties have been recorded for a ruthenium(II) bis(2,2':6',2' '-terpyridine) complex bearing a single ethynylene substituent. The target compound is weakly emissive in fluid solution at room temperature, but both the emission yield and lifetime increase dramatically as the temperature is lowered. As found for the unsubstituted parent complex, the full temperature dependence indicates that the lowest-energy triplet state couples to two higher-energy triplets and to the ground state. Luminescence occurs only from the lowest-energy triplet state, but the radiative and nonradiative decay rates indicate that electron delocalization occurs at the triplet level. Comparison of the target compound with the parent complex indicates that the ethynylene group reduces the size of the electron-vibrational coupling element for nonradiative decay of the lowest-energy triplet state. Although other factors are affected by substitution, this is by far the most important feature with regard to stabilization of the triplet state.     

Ultrafast dynamics of the excited states of 1-(p-nitrophenyl)-2-(hydroxymethyl)pyrrolidine

The dynamics of the excited states of 1-(p-nitrophenyl)-2-(hydroxymethyl)pyrrolidine (p-NPP) has been investigated using the subpicosecond transient absorption spectroscopic technique in different kinds of solvents. Following photoexcitation using 400 nm light, conformational relaxation via twisting of the nitro group, internal conversion (IC) and the intersystem crossing (ISC) processes have been established to be the three major relaxation pathways responsible for the ultrafast deactivation of the excited singlet (S(1)) state. Although the nitro-twisting process has been observed in all kinds of solvents, the relative probability of the occurrence of the other two processes has been found to be extremely sensitive to solvent polarity, because of alteration of the relative energies of the S(1) and the triplet (T(n)) states. In the solvents of lower polarity, the ISC is predominant over the IC process, because of near isoenergeticity of the S(1)(ππ*) and T(3)(nπ*) states. On the other hand, in the solvents of very large polarity, the energy of the S(1)(ππ*) state becomes lower than those of both the T(3)(nπ*) and T(2)(nπ*/ππ*) states, but those of the T(1)(ππ*) state and the IC process to the ground electronic (S(0)) state are predominant over the ISC, and hence the triplet yield is nearly negligible. However, in the solvents of medium polarity, the S(1) and T(2) states become isoenergetic and the deactivation of the S(1) state is directed to both the IC and ISC channels. In the solvents of low and medium polarity, following the ISC process, the excited states undergo IC, vibrational relaxation, and solvation in the triplet manifold. On the other hand, following the IC process in the Franck-Condon region of the S(0) state, the vibrationally hot molecules with the twisted nitro group subsequently undergo the reverse nitro-twisting process via dissipation of the excess vibrational energy to the solvent or vibrational cooling.     

Competition between energy transfer and interligand electron transfer in porphyrin-osmium(II) bis(2,2':6',2' '-terpyridine) dyads

Rapid intramolecular energy transfer occurs from a free-base porphyrin to an attached osmium(II) bis(2,2':6',2' '-terpyridine) complex, most likely by way of the F?rster dipole-dipole mechanism. The initially formed metal-to-ligand, charge-transfer (MLCT) excited-singlet state localized on the metal complex undergoes very fast intersystem crossing to form the corresponding triplet excited state ((3)MLCT). This latter species transfers excitation energy to the (3)pi,pi* triplet state associated with the porphyrin moiety, such that the overall effect is to catalyze intersystem crossing for the porphyrin. Interligand electron transfer (ILET) to the distal terpyridine ligand, for which there is no driving force, competes poorly with triplet energy transfer from the proximal (3)MLCT to the porphyrin. Equipping the distal ligand with an ethynylene residue provides the necessary driving force for ILET and this process now competes effectively with triplet energy transfer to the porphyrin. The rate constants for all the relevant processes have been derived from laser flash photolysis studies.     

Intramolecular photoexcitation dynamics and magnetic field effects in an intermediate-case molecule

Molecular vibration and rotation play a significant role in the intramolecular photoexcitation dynamics of the so-called intermediate-case molecule, and the fluorescence intensity, decay and polarization of s-triazine vapor are shown to depend on the excited rovibronic level of the S₁ state. Fluorescence characteristics are interpreted by assuming three zero-order states: (1) a zero-order singlet state that carries the absorption intensity and emits fluorescence with sharp structure; (2) zero-order singlet states that do not carry the absorption intensity but emit broad fluorescence; and (3) zero-order triplet states. The interaction among these states depends not only on the vibrational level but also on the rotational level excited. It is suggested that the number of triplet states coupled to the singlet state increases with increasing excess vibrational energy. It is also suggested that K-scrambling occurs both in the triplet manifold following intersystem crossing (ISC) and in the singlet manifold following intramolecular vibrational energy redistribution (IVR). The fluorescence intensity and decay of s-triazine vapor are significantly influenced by a magnetic field, and the field effects are interpreted in terms of the spin decoupling in the triplet manifold following ISC; the role of external magnetic fields is to mix the spin sublevels of different rovibronic levels coupled to the excited singlet state. Magnetic depolarization of fluorescence also occurs because of the efficient interaction between the excited singlet state and the triplet state.     

Phototoxic process after rapid photosensitive membrane damage of 5,5"-bis(aminomethyl)-2,2':5',2"-terthiophene dihydrochloride

We report a new aspect of rapid (<30 s) light-induced cell membrane damage photosensitized by 5,5"-bis(aminomethyl)-2,2':5',2"-terthiophene dihydrochloride (BAT), which is a water-soluble alpha-terthienyl analogue, using a high-power laser (light intensity 1.6 W cm(-2)). In this paper, we will discuss the relationship between the exposure time of the cells to the photosensitizer and the phototoxic process. Three toxic processes can be identified: first, a non-light-mediated toxicity dependent on BAT-cell incubation; second, a phototoxicity independent of BAT exposure time when the BAT concentration is in the 2-10-microM range; third, a phototoxicity dependent on BAT exposure time when BAT concentration becomes 20 microM. The cytotoxicity decreases when alpha-tocopherol, an antioxidant, is added to a cell membrane. This pattern of phototoxicity is the typical of a phospholipid peroxidation chain reaction and oxidative damage of membrane proteins triggered by a reactive oxygen species generated by a triplet state of BAT. The BAT exposure time is clearly correlated with the partition of the photosensitizer in the cell membrane and inside the cell.     

Syntheses,structures, and fluxionality of blue luminescent zinc(II) complexes: Zn(2,2',2"-tpa)Cl2, Zn(2,2',2"-tpa)2(O2CCF3)2, and Zn(2,2',3"-tpa)4(O2CCF3)2 (tpa = tripyridylamine)

Three novel Zn(II) complexes containing either 2,2',2"-tripyridylamine (2,2',2"-tpa) or 2,2',3"-tripyridylamine (2,2',3"-tpa) have been synthesized and structurally characterized. Compound 1, Zn(2,2',2"-tpa)Cl2, has a tetrahedral geometry while compounds 2, Zn(2,2',2"-tpa)2(O2CCF3)2, and 3, Zn(2,2',3"-tpa)4(O2CCF3)2, have an octahedral geometry. The 2,2',2"-tpa ligand in 1 and 2 functions as a bidentate ligand, chelating to the zinc center, while the 2,2",3"-tpa ligand in 3 functions as a terminal ligand, binding to the zinc center through the 3-pyridyl nitrogen atom. All three compounds emit a blue color in solution and in the solid state. The emission maxima for the three compounds in solution are at lambda = 422, 426, and 432 nm, respectively. The blue luminescence of the complexes is due to a pi *-->pi transition of the tpa ligand as established by an ab initio calculation on the free ligand 2,2',2"-tpa and complex 1. Compounds 1 and 2 are fluxional in solution owing to an exchange process between the coordinate and noncoordinate 2-pyridyl rings of the 2,2',2"-tpa ligand. Compound 2 is also fluxional owing to a cis-trans isomerization process, as determined by variable-temperature 1H NMR spectroscopic analysis.     

Hf3 cluster is triply (sigma-, pi-, and delta-) aromatic in the lowest D3h, 1A1' state

The extensive search for the global minimum structure of Hf3 at the B3LYP/LANL2DZ level of theory revealed that D3h 3A2' (1a1'(2)1a2'(2)1e'(4)2a1'(2)1e'2) and D3h 1A1' (1a1'(2)2a1'(2)1e'(4)1a2'(2)3a1'2) are the lowest triplet and singlet states, respectively, with the triplet state being the lowest one. However, at the CASSCF(10,14)/Stuttgart+2f1g level of theory these two states are degenerate, indicating that at the higher level of theory the singlet state could be in fact the global minimum structure. The triplet D3h 3A2' (1a1'21a2'(2)1e'(4)2a1'(2)1e'2) structure is doubly (sigma- and pi-) aromatic and the singlet D3h 1A1' (1a1'(2)2a1'(2)1e'(4)1a2'(2)3a1'2) structure is the first reported triply (sigma-, pi-, and delta-) aromatic system.     

Effect of molecular mass on supramolecular organisation of poly(4,4'-dioctyl-2,2':5',2'-terthiophene)

The effect of the chain length on the type and extent of the 2D supramolecular organization in poly(4,4'-dioctyl-2,2':5',2'-terthiophene) (PDOTT) monomolecular layers deposited on highly oriented pyrolytic graphite (HOPG) is studied by scanning tunneling microscopy (STM) and analyzed in terms of molecular modeling. The strictly monodispersed fractions of increasing molecular mass used in this study were obtained by chromatographic fractionation of the crude product of 4,4'-dioctyl-2,2':5',2'-terthiophene oxidative polymerization. STM investigations of PDOTT layers, deposited on HOPG from poly- and monodispersed fractions, show that polydispersity can be considered as a key factor seriously limiting supramolecular ordering. This is a consequence of significant differences in the type of supramolecular order observed for molecules of different chain length. It has been demonstrated that shorter molecules (consisting of 6 and 9 thiophene units) form well-defined two-dimensional islands, while the interactions between longer molecules (consisting of 12 and 15 thiophene units) become anisotropic. Consequently, for higher molecular mass fractions, the supramolecular organization is one-dimensional and consists of more or less separated rows of ordered macromolecules. In this case an increase of the chain length leads to amplification of the intermolecular interactions proceeding via interdigitation of the alkyl substituents of adjacent molecules. Polydispersed fractions show much less ordered organization because of the incompatibility of the supramolecular structures of molecules of different molecular masses. This finding is of crucial importance for the application of polythiophene derivatives in organic and molecular electronics since ordered supramolecular organization constitutes the condition sine qua non of good electrical transport properties.     

碳纳米管-聚(3',4'-亚乙基二氧-2,2':5',2"-三噻吩)复合材料的制备及其电化学性能研究

通过Stille反应合成了3',4'-亚乙基二氧-2,2':5',2"-三噻吩(TET),并以其作为单体,采用化学氧化原位聚合方法在碳纳米管(CNT)的表面包覆新型聚(3',4'-亚乙基二氧.2,2':5',2"-三噻吩)(FTET),制备了PTET-CNT纳米复合材料.通过TEM、SEM和IR对其进行了表征,并利用循环伏安、交流阻抗、恒电流充放电等电化学测试方法,比较研究了复合材料以及碳纳米管在0.1 mol/L四乙基四氟硼酸铵(Et_4NPF_4)的乙腈溶液中的电化学行为.实验结果表明,在电流密度为3 mA/cm~2时,PTET-CNT复合材料的比电容为86 F/g,比原碳纳米管比电容20 F/g提高了3.3倍.基于这种复合材料的电容器的能量密度达到2.02 Wh/kg.