Unique fluorescence behavior of perylenetetracarboxydiimides in polyimide systems

Perylenetetracarboxydiimide (PEDI) molecularly dispersed in polyamic acid (PAA) and polyimide (PI) films has unique fluorescence properties. An originally strong fluorescence of PEDI is efficiently quenched in the PAA films. The systematic variation of the chain structure of the PAA matrices revealed that the aromatic amide groups in the PAA chains function as a quencher. When a PAA derived from 3,4,3′4′-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA), BPDA/PDA, was used as a matrix polymer, the fluorescence of the dye dispersed in the film increased abruptly as imidization of the matrix proceeds. But annealing at temperatures higher than 320°C in the step-heating process caused a gradual decrease in the fluorescence intensity. The decreased intensity results from the dye–PDA units interactions intensified by the denser molecular packing of the matrix polymer chains. PEDI shows significant dependence of the fluorescence intensity on the chain structure of the PI matrices. In the various PI films containing a fixed diamine component, the dye fluorescence intensity reduces linearly with an increase in the intramolecular charge transfer ability of the PI matrices. From the result, we propose a fluorescence quenching mechanism through multistep electron transfer processes. The BPDA/PDA polyimide matrix leads to a strong PEDI fluorescence whereas the pyromellitic dianhydride (PMDA)-based PI matrices do not. For the blends composed of these PIs, the fluorescence of PEDI bound into the main chains provides a valuable indicator of the miscibility on the molecular level. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 827–840, 1998     

Preparation and absorption spectrum studies of aromatic and alicyclic poly(amide acid) ammonium salts in water and DMF and in films

A series of ammonium salts of poly(amide acid)s (PAS) were prepared from various poly(amide acid)s (PAA) with tertiary amines. The solubility of poly(amide acid) ammonium salts prepared from PAA(PMDA/ODA) in water is related to the ion concentration of tertiary amines. In order to elucidate the influence of the chemical structures of poly(amide acid)s and poly(amide acid) ammonium salts on their absorption spectra, pyromellitic dianhydride (PMDA), 3,3′,4,4 ′-biphenyltetracarboxylic dianhydride (BPDA), and 3,3′,4,4 ′-benzophenonetetracarboxylic dianhydride (BTDA) were chosen to react with p-phenylenediamine (PDA) and (4,4′-diaminodicyclohexyl)methane (DCHM) to give three kinds of aromatic PAAs and three kinds of alicyclic PAAs. The corresponding PASs were prepared by the reaction of PAAs with triethanolamine (TEA). Their ultraviolet–visible (UV–vis) absorption spectra were investigated compared to those of model compounds. A transparent film without absorption above 320 nm was obtained for PAS(PMDA/DCHM). The difference in absorption spectra of PAS(PMDA/PDA) from that of PAS(PMDA/DCHM) can be related to the existence of intra- and intermolecular charge transfer (CT) for PAS(PMDA/PDA). The absorption spectra of PASs with PDA in films are red shifted compared to those of corresponding PAAs in films, while the absorption spectra of PASs in water are blue shifted compared to those of corresponding PAAs in DMF. No differences in the absorption spectra of PAAs and PASs were found in DMF/H₂O (9/1) mixed solvent. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1329–1340, 1998     

Relaxation of photo-excitations in films of oligo- and poly-(para-phenylene vinylene) derivatives

The photo-luminescence from solid films of poly(para-phenylene vinylene) polymers and an oligomeric model system, consisting of seven repeat units, are investigated at low temperature (8 K) using time-resolved spectroscopic techniques. Results are compared to those for the materials in solution. In the case of the oligomer, the shape of the visible absorption band observed for the film is quite different from the band shape for the polymer in frozen solution and is characteristic of H-type aggregates. Theoretical models are presented describing the dependence of the band shape of absorption and emission spectra on intermolecular excited state interactions, electron-vibration coupling and disorder represented by distributions of the molecular excitation and intermolecular interaction energies. Using these models, it is concluded that intermolecular interactions in the film of the oligomer are strong (1400 cm⁻¹), and the disorder low, implying delocalization of the excitation over several molecules. In accordance with these models the fluorescence lifetime for the film (2 ns) is considerably longer than for isolated molecules in solution (0.45 ns). The emission spectra of the film, taken early after excitation, are consistent with delocalization of the excitation over several molecules. A time-dependent red shift of the fluorescence band is observed and interpreted in terms of migration of localized excitations between disorder induced trap sites, which exist in the low energy tail of the density of excited states. For the polymers, differences between the shape of the absorption bands of solid film and frozen solution are smaller than for the oligomer indicating that interchain interactions that are, on average, weaker than for the oligomer. For the polymer films, a time-dependent red shift of the emission is observed and fluorescence depolarization measurements provide direct evidence for migration of the photo-excitations between trap sites. For one polymer, a time dependent change in the band shape of the fluorescence after pulsed excitation is observed with the band shape of the long-lived emission being compatible with that expected for an excitation delocalized over at least two, nearly parallel aligned, chains. For a second polymer, the emission band shape and its time evolution indicate that the major part of the fluorescence originates from disorder induced luminescent sites. These results indicate that the spectroscopic properties of films of π-conjugated polymer critically depend on parameters such as density of defects and excited state interchain interaction energy.     

Improvement of thermoplasticity for s‐BPDA/PDA by copolymerization and blend with novel asymmetric BPDA‐based polyimides

Asymmetric biphenyl type polyimides (PI) derived from 2,3,3′,4′‐biphenyltetracarboxylic dianhydride (a‐BPDA) and p‐phenylenediamine (PDA) or 4,4′‐oxydianiline (ODA) show higher T_gs, and much better thermoplasticity than the corresponding isomeric PIs from symmetric 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA). In addition, a‐BPDA‐derived PIs are completely amorphous owing to their bent chain structures and highly distorted conformations, whereas the PIs from s‐BPDA are semicrystalline. a‐BPDA‐derived PIs possessing these properties or the a‐BPDA monomer were used as a flexible blend component or a comonomer to improve the insufficient thermoplasticity of semirigid s‐BPDA/PDA homo polymer. The blends composed of s‐BPDA/PDA (80%) with a‐BPDA‐derived PIs (20%), as well as the s‐BPDA/PDA‐based copolymer containing 20% a‐BPDA, showed a certain extent of thermoplasticity above the T_gs without causing a decrease in T_g. In addition, these blends and copolymer provided comparatively low thermal expansion coefficient (ca. 18 ppm). The improved film properties for the blends are related to good blend miscibility. On the other hand, when s‐BPDA/ODA was used as a flexible matrix polymer instead of a‐BPDA‐derived PIs, the 80/20 blend film annealed at 400°C exhibited no prominent softening at the T_g. This result arises from annealing‐induced crystallization of the flexible s‐BPDA/ODA component. Thus, these results revealed that a‐BPDA‐derived PIs are promising candidates as matrix polymers for semirigid s‐BPDA/PDA for the present purpose. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2499–2511, 1999     

Spectroscopic and optical characterization of porphyrin chromophores incorporated into ultrathin polyimide films

Polyamic acid (PAA) containing free-base porphyrin and zinc(II) porphyrin chromophores was synthesized by copolymerization of diphenylether-type tetracarboxylic dianhydride and diamines. The monolayer of the alkylamine salts of PAA (PAASs) at the air/water interface was deposited on solid substrates by the Langmuir-Blodgett (LB) technique. The PAAS LB films thus obtained were converted to polyimide (PI) LB films by chemical treatment. The fluorescence of porphyrin moieties in the PI LB film was observed, because of the weak electron-accepting properties of the diphenylether unit. Therefore, the photophysically important processes, such as photoinduced electron transfer, excitation energy transfer, and excitation energy migration could be investigated in relation to the layered nanostructures of the ultrathin PI films. The fluorescence spectrum suggested that the aggregation of porphyrin moieties in the PI LB films was effectively prevented by the use of polymeric films. The surface plasmon (SP) measurement showed that the thickness of the monolayers was 0.9-1.0 nm for PAAS films and 0.32-0.40 nm on average for PI LB films. The absorption dichroism of the Soret band of porphyrin indicated that porphyrin moieties in the PAAS and PI LB films are oriented in parallel with the substrate. These results showed that the orientation and the spatial distribution of porphyrin units can be efficiently regulated in the PI LB films in a nanometer dimension.     

卟啉类L-B膜分子间相互作用的光谱研究

以无取代的meso-四-(4-N)-吡啶基卟啉及其过渡族金属(主要Cu~(2+)、Zn~(2+))络合物制备L-B膜,以近紫外-可见吸收光谱和荧光光谱为手段,研究叶啉类分子在氯仿溶液中,L-B膜状态下以及固态状态下的相互作用。探讨分子聚集体的存在对光谱性质的影响。 为了研究叶咻类分子间的相互作用及其对光谱性质的影响,我们首先分析了叶啉在CHCl_3溶液中及固态状态下的近紫外-可见吸收光谱和荧光光谱。并将其与叶啉类分子的L-B膜作比较。结果表明,卟啉类的Soret吸收带带宽及峰位置在三种状态下均不相同,L-B膜的情况介于溶液中的和固体下的情况之间,说明了在L-B膜中,卟啉分子存在着某种形式的聚集体,且在这种聚集体中分子间的相互作用程度比固体弱,可以认为L-B膜上的分子呈准晶体状态。     

Dendritic oligothiophenes terminated with tris(alkyloxy)phenylethynyl tails: synthesis, physical properties, and self-assembly

Three-dimensional (3D) π-conjugated dendritic oligothiophenes up to a third generation have been functionalized with tris(decyloxy)phenylethynyl tails at the periphery. The first-generation compounds (3 T-p-Ph-C10 and 6 T-p-Ph-C10) were synthesized by palladium-catalyzed Sonogashira coupling reactions, whereas the higher generation products were synthesized by palladium-catalyzed Suzuki coupling reactions in a divergent approach. The optical and electrochemical properties were investigated by UV/Vis absorption, fluorescence spectroscopy, and cyclic voltammetry. The results revealed that the terminal tris(alkyloxy)phenylethynyl groups are conjugated to the branched oligothiophene core, yielding redshifted absorption and fluorescence spectra and reduced optical band gaps relative to the dendritic oligothiophene core. A structural study revealed a close relationship between the type of supramolecular organization and the size of the oligothiophene core. The first-generation compounds 3 T-p-Ph-C10 and 6 T-p-Ph-C10 displayed columnar phases in the bulk state, which was confirmed by two-dimensional wide-angle X-ray scattering (2D WAXS) measurements. The self-assembly into columnar stacks has mainly been attributed to phase separation between the rigid thiophene cores and the flexible side-chains assisted by minor π-stacking interactions between the conjugated dendritic oligothiophene units. The high-generation compounds, however, showed less ordered structures in the solid state.     

四(4,4',4'',4'''-N,N-二氨基)四苯乙烯光致发光与分子的构象效应

利用还原偶联方法合成出新化合物四(4,4',4',4''-N,N-二氨基)四苯乙烯（ TDETE）。通过测定该化合物在溶液、掺杂聚合物中及晶体粉末的稳态-瞬态荧光光 谱、荧光量子产率和辐射衰变速率常数等。讨论了分子的构象效应等因素对TDETE 光致发光行为的影响。在一定浓度下TDETE溶液存在着三个发光带,分别为全扭曲 构象分子（位于345nm附近的发光I带）、半扭曲构象分子（位于430nm附近的发光 II带）和激基缔合物（530发光III带）的辐射衰变所致。在聚合物（PMMA）中,一 方面由于分子单键的自由旋转扭曲受到遏制,表现为II带的辐射衰变速率常数(kf 值)增大、同时非辐射衰变速率常数knf值减小;另一方面,TDETE分子之间相互作 用得到加强而有利一缔合物形成,结果,使发光II带和III带合二为一出现强而宽 的发射峰,荧光量子产率从溶液中的0.055提高到0.855。此外,在PMM介制裁中观 测到TDETE分子聚集体在626nm处的发光带（IV）,数粉末态中聚集体IV带的强度骤 增,峰值波长红移至650nm。     

Blue-emitting ZnO sol and film obtained by sol-gel process

In this paper, bright blue-emitting ZnO sol and film were prepared by sol-gel process and the luminescent properties were investigated. The absorption spectrum of the sol consists of a wide band with two steps in the long wavelength region. The sol and film show a single wide blue-emission band under excitation of UV light, while the excitation spectra are composed by multiple bands. The quantum yield of the ZnO sol is 0.52 when the excitation wavelength is 348 nm. The particle size of the film is smaller than 10 nm, which results in the fine structure of the absorption and excitation spectra.     

High strength electrospun polymer nanofibers made from BPDA-PDA polyimide

A series of high molecular weight PI precursors, poly(p-phenylene biphenyltetracarboxamide acid), were synthesized from 3,4,3′,4′-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA) by using intense mechanical stirring at −15 to 0 °C for 48-72 h. The as-synthesized PI precursor solution was used to make BPDA/PDA polyimide thin films and electrospun nanofibers. IR, Ostward Viscometer, CMT-8102 Electromechanical Universal Testing Machine and scanning electron microscope (SEM) were used for the characterizations of the as-synthesized PI precursor, PI films and nanofiber sheets. The high molecular weight BPDA/PDA PI thin films and electrospun nanofiber sheets possess excellent mechanical properties of up to 900 MPa tensile strength with up to 18.0 GPa E-modulus and up to 210 MPa tensile strength with up to 2.5 GPa E-modulus, respectively.     

Energy transfer in calixarene-based cofacial-positioned perylene bisimide arrays

The synthesis of multichromophoric perylene bisimide-calix[4]arene arrays with up to five perylene units (containing orange, violet, and green perylene bisimide chromophores) and of monochromophoric model compounds was achieved by subsequent imidization of mono-Boc functionalized calix[4]arene linkers with three different types of perylene bisimide dye units. The optical properties of all compounds were studied with UV/vis absorption and steady state and time-resolved fluorescence spectroscopy. Upon excitation of the inner orange dye at 490 nm of array 3, strong fluorescence emission of the outer green perylene bisimide (PBI) chromophore at 744 nm is observed. The fluorescence excitation spectra of compounds 3 and 4 (lambdadet = 850 nm) show all absorption bands of the parent chromophores (e.g., all perylene units contribute to the emission from S1 state of the green PBI). Thus, the fluorescence emission and excitation spectra as well as time-resolved data of fluorescence lifetimes in the absence (tauD = 5.1 ns) and in the presence of an acceptor (tauDA = 0.8 ns) suggest efficient energy transfer processes between the perylene bisimide dye units. For the bichromophoric array 4, the energy transfer rate is calculated to a value of 1.05 x 109 s-1. These results demonstrate highly efficient energy transfer in cofacially assembled dye arrays.     

Photoconductivity of a polyimide with an alicyclic diamine: Charge carrier photogeneration in the mixed layer packing arrangement

Photoconduction mechanism of a polyimide with an alicyclic diamine, PI(PMDA/DCHM), prepared from pyromellitic dianhydride (PMDA) and 4,4′-diaminodicyclohexylmethane (DCHM) was investigated. Its UV absorption spectra, fluorescence spectra, photoconductivity, and annealing effects on the photocurrent generation were measured and compared to those of CPD, N,N′-dicyclohexylpyromellitic diimide, and PI(PMDA/DMDHM) prepared from PMDA and 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane (DMDHM). Photoconductivity of PI(PMDA/DCHM) depends upon the degree of molecular packing between polymer backbones. PI(PMDA/DMDHM) has no photoconductivity, probably due to a barrier to their intermolecular packing by the existence of two methyl substituents. Photoconductivity of PI(PMDA/DCHM) would be the result of the weak intermolecular interaction formed by mixed layer packing arrangement between pyromellitic moiety of one polymer backbone and N-cyclohexyl ring of another one in the ground state. Radiation absorption of this weak intermolecular interaction immediately forms a charge–transfer complex in the excited state and produces radical cation and anion charge carriers, which lead to the photoconductivity in the bulk polyimide film of PI(PMDA/DCHM). © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1433–1442, 1998     

Charge-transfer-type fluorescence of 4-(1H-pyrrol-1-yl)benzonitrile (PBN) and N-phenylpyrrole (PP) in cryogenic matrixes: evidence for direct excitation of the CT band

The fluorescence spectrum of PBN in a neat argon matrix is excitation-wavelength-dependent: at short excitation wavelengths, it consists of dual emission assigned to a charge-transfer (CT) state and a much weaker band assigned to the locally excited (LE) state. The CT emission is broad and almost completely devoid of vibrational structure, whereas the LE band is characterized by vibrationally resolved emission. At long excitation wavelengths, only CT emission is observed, indicating that the CT state is populated directly by light absorption and not via the LE state. Comparison with jet-cooled spectra of the bare molecule allows the unambiguous assignment of the LE spectrum and the location of the 0,0 band. The matrix LE emission spectrum is blue-shifted with respect to that of the gas phase, showing that the dipole moment of the LE state is smaller than that of the ground state. The fluorescence spectrum of PBN in an argon matrix does not change appreciably when acetonitrile (AN) is added to the matrix, in contrast to the case of N-phenylpyrrol (PP) (Schweke, D.; Haas, Y. J. Phys. Chem. A 2003, 107, 9554), for which addition of AN results in the appearance of two well separated emission bands. The different photophysical behaviors of PP and PBN in an argon matrix (and in supersonic jets) are analyzed by a simple model that considers the restriction of large-amplitude motions in the matrix. The implications of these low-temperature studies for understanding the properties of these systems in liquid solution are discussed.     

Fluorescence of perylene- and naphthalene-containing polyimides: Evidence of molecular aggregation and chain coiling in chloroform solution

Fluorescence of several new polyimides in which neighboring imides are linked by a N-N bond was examined in chloroform solutions. For the naphthalene-containing polyimide 1 , analysis of the emission, excitation, and absorption spectra at different concentrations showed the existence of a ground-state intermolecular charge transfer (CT) complex due to chain association and aggregation. For the perylene-containing polyimides 3-6 , the fluorescence was characterized by a low energy band superimposed on the normal perylenediimide bands. This was interpreted as arising from a CT interaction between electron donor-acceptor pairs on the polymers backbone of the same chain, revealing certain degrees of chain coiling of these polymers in solution. © 1995 John Wiley & Sons, Inc.     

Improved Spectral Coverage and Fluorescence Quenching in Donor–acceptor Systems Involving Indolo[3‐2‐b]carbazole and Boron‐dipyrromethene or Diketopyrrolopyrrole

A novel π‐conjugated triad and a polymer incorporating indolo[3,2‐b]‐carbazole (ICZ) and 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) were synthesized via a Sonogashira coupling. Compared to the parent BODIPY the absorption and fluorescence spectrum were for both compounds broader and redshifted. The redshift of the fluorescence and the decrease of the fluorescence quantum yield and decay time upon increasing solvent polarity were attributed to the formation of a partial charge‐transfer state. Upon excitation in the ICZ absorption band the ICZ fluorescence was quenched in both compounds mainly due to energy transfer to the BODIPY moiety. In a similar ICZ–π–DPP polymer (where DPP is diketopyrrolopyrrole), a smaller redshift of the absorption and fluorescence spectra compared to the parent DPP was observed. A less efficient quenching of the ICZ fluorescence in the ICZ–π–DPP polymer could be related to the unfavorable orientation of the transition dipoles of ICZ and DPP. The rate constant for energy transfer was for all compounds an order of magnitude smaller than predicted by Förster theory. While in a solid film of the triad a further redshift of the absorption maximum of nearly 100 nm was observed, no such shift was observed for the ICZ–π–BODIPY polymer.     

The electronic spectra and excited state dipole moment of 2-fluoropyridine

The electronic absorption spectrum in the vapour state and in solution in different solvents in the region 3000–1900 Å and the fluorescence and phosphorescence emission spectra in ethanol or cyclohexane at 77 K have been studied for 2-fluoropyridine and analysed. Two systems of absorption band corresponding to the π→π* transition II and π→π* transition III have been observed and the excited state dipole moments have been determined from the solvent-induced shifts of the electronic absorption bands. The half-life of phosphorescence in cyclohexane at 77 K is found to be 3.5 s.     

Dual fluorescence of graphene oxide: a time-resolved study

The fluorescence properties of graphene oxide (GO) was studied by recording the fluorescence lifetime, fluorescence emission, and excitation spectra, as well as UV-visible and near-IR absorption spectra. For the first time, we showed that a blue band (ca. 440 nm) and a long wavelength (LW) band (ca. 700 nm) are coexistent, which can be recorded simultaneously by controlling concentration, excitation wavelength, and pH values. Two bands are closely related by the protonation or deprotonation of GO. The blue band is favored by low GO concentration, short excitation wavelength, and high pH value, while the LW band is favored by low pH and long excitation wavelength. To reveal the nature of the dual emission of GO, the fluorescence lifetimes under various conditions were also measured. The blue band contains three emitting components; one of them has a lifetime as long as 10 ns, and its emitting intensity is fairly sensitive to pH, showing the potential for applications in sensing H(+) and fluorescence lifetime imaging. Combining the results under various conditions, we conclude that the electronic transition for this component is very likely due to n-π* transition. The LW band contains two main emitting components (0.2 and 2.1 ns) that also appear in the blue band as minor contributors; the related emission is assigned to π-π* transition. In summary, GO emission is of broadband (300-1250 nm), long-lived, pH sensitive, and excitation wavelength dependent. This makes it easily tailored for versatile applications.     

The Si-B chromophore: A joint experimental and theoretical investigation

Silylboranes with aromatic substituents linked to boron and silicon exhibit an unexpected absorption band in the UV-Vis spectral region. When polar groups were introduced, a marked solvatochromic effect was observed in their fluorescence emission spectra, revealing a strong excited state dipole moment. Semi-empirical MNDO/d and AM1 calculations showed that, upon UV excitation, the polarity of the Si-B bond increased and the aromatic π-electrons migrated toward the Si-B bond, consistent with experimental observations.     

Femtosecond time-resolved photophysics of 1,4,5,8-naphthalene diimides

The photophysical properties of a tetrahedral molecule with naphthalene diimide (NDI) moieties and of two model compounds were investigated. The absorption and fluorescence spectra of dialkyl-substituted NDI are in agreement with literature. While the absorption spectra of phenyl-substituted molecules are similar to all other NDIs, their fluorescence showed a broad band between 500 and 650 nm. This band is sensitive to the polarity of the solvent and is attributed to a CT state. The absorption spectra and lifetime (10+/-2 ps) of the electronically excited singlet state of a dialkyl-substituted NDI was determined by femtosecond transient absorption spectroscopy, and the latter was confirmed by picosecond fluorescence spectroscopy. Nanosecond flash photolysis showed the subsequent formation of the triplet state. The presence of a phenyl substituent on the imide nitrogen of NDI resulted in faster deactivation of the singlet state (lifetime 0.5-1 ps). This is attributed to the formation of a short-lived CT state, which decays to the local triplet state. The faster deactivation was confirmed by fluorescence lifetime measurements in solution and in a low-temperature methyl-tetrahydrofuran glass.