Synthesis, structure, and photophysical and electrochemical properties of a pi-stacked polymer

Dibenzofulvene (DBF) was polymerized using anionic initiators to afford a vinyl polymer. Oligo(DBF)s having from two to eight side-chain fluorene moieties bearing different chain-terminal groups were isolated by preparative size-exclusion chromatography. The structures of the isolated oligomers were revealed by single-crystal X-ray and (1)H NMR analyses. Both in solution and in crystal, the in-chain fluorene moieties stacked on top of each other, while the terminal conformation varied depending on the terminal group. These conformational characteristics were supported by molecular mechanics and dynamics calculations. The oligomers and polymers indicated hypochromism and red shift in UV absorption spectra and exclusive excimer emission in fluorescence spectra. In addition, reduced oxidation potentials were observed for the oligomers in electrochemical analyses, which suggests charge delocalization over the pi-stacked electron systems. The photophysical and electrochemical effects increased with the chain length of the oligomers and leveled off around the chain length of an oligomer consisting of five fluorene units.     

Zigzag molecules from pyrene-modified carbazole oligomers: synthesis, characterization, and application in OLEDs

A series of monodisperse, pyrene-modified oligocarbazoles were synthesized and fully characterized. Carbazoles were linked by ethynylene through the 3- and 6-positions, forming a zigzag molecular backbone and stable, size-independent absorption, and emission were observed from these oligomers in solutions because their conjugation length was confined. Oligomers with pyrene exhibited much higher fluorescence quantum yields than those of oligomers without it. Different positions of pyrene in the oligocarbazole main chain resulted in a remarkable change in absorption and emission spectra. Moreover, devices with four different architectures (types 1-4) based on these oligomers were fabricated and investigated. Pyrene-modified carbazole oligomers exhibited bifunctional properties (light-emitting and hole-transport). Moreover, these devices showed moderate performances; for example,the device based on Cz3PyCz3 presented an external quantum efficiency of 0.69% and a maximum brightness of 1782 cd/m2 at 13.5 V, which indicated these oligomers were promising optoelectric materials.     

Synthesis and characterization of monodisperse oligo(fluorene-co-bithiophene)s

A series of monodisperse oligo(9,9-di-n-octylfluorene-co-bithiophene)s (OFbTs) with molecular lengths of up to 19.5 nm and molecular weights up to 7025 g mol(-1) has been synthesized by a divergent/convergent approach involving Stille coupling reactions. Stille coupling is quite efficient in preparing this class of oligomers, and even the molecule with nine fluorene units and eight bithiophene units (F9Th16) can be synthesized in a yield as high as 70 %. Because of easy functionalization of the thiophene ring at its alpha position, no additional protecting group allowing activation for further reaction is necessary. However, the synthetic routes must be optimized to eliminate contamination of the targeting compounds with the homocoupling product of the organotin reagents. Synthesis of the longest oligomer F13Th24 in a relative large quantity is limited by its low yield due to the pronounced ligand-exchange side reactions of the starting materials and reaction intermediates. All oligomers longer than F4Th6 are nematic mesomorphs and exhibit enhanced glass transition temperature and clearing point with increasing molecular length, as revealed by differential scanning calorimetry and polarizing optical microscopy. Absorption and photoluminescence (PL) measurements reveal that OFbTs are well-conjugated systems with an effective conjugation length longer than the length of F13Th24.     

Conjugated polymers containing electron‐transporting,hole‐transporting,and light‐emitting units in the polymer main chain

Conjugated polymers containing electron‐transporting, hole‐transporting, and blue light‐emitting units were synthesized by Suzuki polycondensation. These copolymers exhibited excellent thermal and optical stability. Optical investigation indicated that the incorporation of the spirobifluorene units in the polymer main chain could markedly increase the effective conjugation length of polymers. Electrochemical studies showed that the incorporation of spirobifluorene unit could raise the electrochemical stability and improve the electron‐ and hole‐injecting abilities. The electroluminescent results also showed that the introducing of spirobifluorene units could significantly improve the device performance. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1349–1356, 2008     

Synthesis and electronic properties of monodisperse oligophenothiazines

Starting from N-hexylphenothiazine, a versatile construction kit of brominated and borylated phenothiazines can be easily prepared by a sequence of bromination, bromo-lithium exchange/borylation, and Suzuki coupling. Subsequent Suzuki arylation of the building blocks gives soluble, monodisperse, and structurally well defined oligophenothiazines in good yields. The molecular weights at the peak maximum (Mp), obtained by GPC (gel permeation chromatography), and the actual molecular weights of the oligomer series, obtained by mass spectrometry, show excellent correlation. A QM/MM conformational analysis for the complete series reveals that the obvious butterfly-shaped phenothiazine structure multiplies and significantly reduces the hydrodynamic volume of the oligomers. The electronic properties (absorption and emission spectroscopy and cyclic voltammetry) give reasonable correlations with the chain length. With regard to the emission maxima, the effective conjugation length is already reached with the hexamer. Oligophenothiazines are highly fluorescent, with high fluorescence quantum yields, and are simultaneously highly electroactive, with low oxidation potentials.     

Synthesis and photophysical properties of monodisperse oligo(9,9-di-n-octylfluorene-2,7-vinylene)s functionalized anthracenes

Four new well-defined monodisperse linear oligofluorenes with anthracene core An-OFVn (n = 1-4) have been synthesized through Heck and Wittig reaction. These conjugated oligomers exhibit good solubility in common organic solvents. It is found that the conjugation length of the oligomers can be extended and the formation of excimers can be suppressed with increasing the number of fluorene-vinylene units linked in the 9,10-positions of anthracene.     

Applying the oligomer approach to luminescent conjugated organoboranes

A series of highly luminescent monodisperse fluoreneborane oligomers (n=1-6) were prepared using a new iterative synthetic procedure that takes advantage of the highly selective and differential reactivity of bromoboranes with arylsilanes and arylstannanes. Cyclic and square wave voltammetry revealed a gradual decrease of the LUMO energy levels with increasing chain length, while absorption and emission data showed a bathochromic shift and increase in quantum efficiency. An extended conjugation length of n(ECL)=5 was derived.     

Synthesis and physical investigation of donor-donor and acceptor-acceptor end-functionalized monodisperse poly(triacetylene) oligomers

Two series of monodisperse, terminally donor-donor [D-D, D=4-(dimethylamino)phenyl] and acceptor-acceptor [A-A, A=4-nitrophenyl] functionalized poly(triacetylene) (PTA) oligomers ranging from monomer to hexamer were synthesized by oxidative Hay oligomerization under end-capping conditions. The corresponding D-D and A-A end-substituted polymers with an average degree of polymerization (DP) of n approximately 18 and n approximately 12, respectively, were also prepared and served as reference points for the corresponding infinitely long polymers. These terminally functionalized PTA oligomers and polymers are yellow- to orange-colored compounds, displaying excellent solubility in aprotic solvents with melting points above 200 degrees C for the hexamers. For the 4-(dimethylamino)phenyl substituted compounds, a consistent first oxidation potential around +0.42 V versus Fc/Fc+ (ferrocene/ferricinium) was observed, whereas the 4-nitrophenyl functionalized systems underwent a reversible reductive two-electron transfer around -1.40V versus Fc/Fc+. The nature of the end-groups has a dramatic influence on the electronic absorption spectra. Saturation of the linear optical properties in the D-D series occurs at significantly shorter chain-length [effective conjugation length (ECL) of n approximately 4 monomer units] than in the A-A substituted or the previously reported Me3Si- and Et3Si-end-capped PTA oligomer series (ECL: n approximately 10 monomer units). Similar observations with respect to the ECL were made by measurement of the Raman-active v(C triple bound C) stretches. Third-harmonic generation (THG) and degenerate four-wave mixing (DFWM) experiments showed that shorter oligomers of terminally D-D or A-A functionalized PTAs display higher second hyperpolarizabilities gamma than the corresponding R3Si-end-capped series (R=alkyl). Moreover, they disclose a distinct peak of the nonlinearity per monomer unit at intermediate backbone lengths. In THG experiments, the second hyperpolarizabilities for long D/A-functionalized PTA oligomers attained the same saturation values as observed for the corresponding R3Si-end-capped rods. The nonlinearities measured by DFWM of the D-D and A-A substituted PTAs were found to be larger than for the silylated ones, which can be explained by the closeness of the two-photon resonance.     

BN-Embedded Polycyclic Aromatic Hydrocarbon Oligomers: Synthesis,Aromaticity, and Reactivity

BN-embedded oligomers with different pairs of BN units were synthesized by electrophilic borylation. Up to four pairs of BN units were incorporated in the large polycyclic aromatic hydrocarbons (PAHs). Their geometric, photophysical, electrochemical, and Lewis acidic properties were investigated by X-ray crystallography, optical spectroscopy, and cyclic voltammetry. The B−N bonds show delocalized double-bond characteristics and the conjugation can be extended through the trans-orientated aromatic azaborine units. Calculations reveal the relatively lower aromaticity for the inner azaborine rings in the BN-embedded PAH oligomers. The frontier orbitals of the longer oligomers are delocalized over the inner aromatic rings. Consequently, the inner moieties of the BN-embedded PAH oligomers are more active than the outer parts. This is confirmed by a simple oxidation reaction, which has significant effects on the aromaticity and the intramolecular charge-transfer interactions.     

Structural, optical, and electronic properties of a series of 3,4-propylenedioxythiophene oligomers in neutral and various oxidation States

A series of 3,4-propylenedioxythiophene (ProDOT) oligomers (nP(Hex)) with dihexyl side chains and methylthio end-capping units was synthesized as a model of poly(3,4-alkylenedioxythiophene)s. The slope of the linear relationship between the energy of the absorption maxima of nP(Hex) in the neutral states and the reciprocal of the number of monomer units (1/n) was found to be comparable to that of 3,4-ethylenedioxythiophene (EDOT) oligomers, suggesting that both the ProDOT and the EDOT oligomers have a similar effective conjugation. In cyclic voltammetry measurements, both the first and second oxidation waves and the third and fourth waves were shown to merge into one peak with increasing chain length. The stepwise chemical oxidations of nP(Hex) with SbCl(5) in CH(2)Cl(2) at room temperature gave their stable cationic species in various oxidation states, and it was found that only the radical cations (polarons) have an obvious absorption band in the visible region. Interestingly, when the absorption spectra of tetramer radical cation 4P(Hex)(+·) were measured at low temperatures, reversible disproportionation into dication 4P(Hex)(2+) and neutral species 4P(Hex) was observed in addition to π-dimer formation. Furthermore, the radical cations of the longer oligomers showed only the disproportionation reaction. From the comparisons of the results of experiments and the theoretical calculations of the dications, 6P(Hex)(2+) was found to have a closed-shell nature, and only a weak singlet biradical character appeared even in longer oligomers 10P(Hex)(2+) and 12P(Hex)(2+). Overall, the electron-donating dioxy substituents are considered to stabilize high p-doping levels with closed-shell dication (bipolaron) structures in poly(3,4-alkylenedioxythiophene)s, which enables the transparency properties of the polymers.     

BN‐Embedded Polycyclic Aromatic Hydrocarbon Oligomers: Synthesis,Aromaticity, and Reactivity

BN‐embedded oligomers with different pairs of BN units were synthesized by electrophilic borylation. Up to four pairs of BN units were incorporated in the large polycyclic aromatic hydrocarbons (PAHs). Their geometric, photophysical, electrochemical, and Lewis acidic properties were investigated by X‐ray crystallography, optical spectroscopy, and cyclic voltammetry. The B?N bonds show delocalized double‐bond characteristics and the conjugation can be extended through the trans‐orientated aromatic azaborine units. Calculations reveal the relatively lower aromaticity for the inner azaborine rings in the BN‐embedded PAH oligomers. The frontier orbitals of the longer oligomers are delocalized over the inner aromatic rings. Consequently, the inner moieties of the BN‐embedded PAH oligomers are more active than the outer parts. This is confirmed by a simple oxidation reaction, which has significant effects on the aromaticity and the intramolecular charge‐transfer interactions.     

Modeling of Structure and Nonlinear Optical Activity of Epoxy-Based Oligomers with Dendritic Multichromophore Fragments

Summary: Epoxy-based oligomers having length up to four units with dendritic chromophore-containing fragments covalently attached through spacers to the bearing chain are studied. The structure of the oligomers was obtained in the course of conformational search by Monte-Carlo method, the distribution of the torsion angles values in the dendritic fragment was examined by molecular dynamics. The nonlinear-optical response of the studied oligomers and dendritic chromophore fragments was calculated by the TDHF method at AM1 level. Intradendron cross-linking of chromophore groups is investigated, diphenylmethandiisocyanate used as hardening agent. Cross-linking is shown to decrease the angles between the chromophores in the dendron, thus providing enhanced nonlinear-optical characteristics of the oligomer. Stacking-like arrangement of chromophore groups, observed in variety of oligomers, is investigated in the framework of topological analysis of electron charge density, and Van-der-Waals interactions are found to be responsible for the stacking effect.     

Solid-phase synthesis of m-phenylene ethynylene heterosequence oligomers

Both homo- and heterosequence m-phenylene ethynylene oligomers are synthesized using a conceptually simple iterative solid-phase strategy. Oligomers are attached to Merrifield's resin through a known triazene-type linkage. The phenylene ethynylene molecular backbone is constructed through a series of palladium-mediated cross-coupling reactions. The strategy employs two types of monomers that bear orthogonal reactivity, one being a monoprotected bisethynyl arene and the other being a 3-bromo-5-iodo arene. The catalyst conditions are tailored to the requirements of each monomer type. The monoprotected bisethynyl arene is coupled to the growing chain in 2 h at room temperature using a Pd(I) dimer precatalyst ((t)Bu3P(Pd(mu-Cl)(mu-2-methyl allyl)Pd)P(t)Bu3) in conjunction with ZnBr2 and diisopropylamine. In alternate steps, the resin is deprotected in situ with TBAF and coupled to the 3-bromo-5-iodo arene using the iodo selective Pd(tri-2-furylphosphine)4 catalyst in conjunction with CuI and piperidine; this reaction is also completed in 2 h at room temperature. These cross-coupling events are alternated until an oligomer of the desired length is achieved. The oligomer is then cleaved from the resin using CH(2)I(2)/I(2) at 110 degrees C and purified using preparatory GPC. Using this method, a series of homo- and heterosequence oligomers up to 12 units in length in excellent yield and purity were synthesized on the 100 mg scale. Longer oligomers were attempted; however, deletion sequences were found in oligomers longer than 12 units.     

Synthesis and Characterization of 2,7‐Linked Carbazole Oligomers

A set of monodisperse 2,7‐linked carbazole oligomers (3‐mer, 5‐mer, 7‐mer, and 9‐mer) was synthesized, and their photophysical, electrochemical, and thermal properties were investigated. In solutions, these oligomers exhibited bright blue emission with almost quantitative fluorescence quantum yield. The emission spectra of these oligomers in films are quite different. 3‐Mer and 5‐mer exhibited featureless emission spectra, whereas 7‐mer and 9‐mer showed well‐resolved emission spectra.     

Through versus cross electron delocalization in polytriacetylene oligomers: a computational analysis.

Herein, we report a systematic theoretical investigation of the molecular and electronic properties of unsubstituted polytriacetylene (PTA) and iso-polytriacetylene (iso-PTA) oligomers, which are characterized by through and cross pi-conjugation pathways, respectively. The goal of the study is to compare through versus cross conjugation on the basis of the computed molecular geometries of the neutral, anionic, and cationic species, the electron affinities, ionization potentials, excitation energies, and nonlinear optical properties for oligomers up to the nonamer. Differences in the effective conjugation length are directly related to electron delocalization in cross- and through-conjugated pathways. As in the through-conjugated oligomers, that is, the PTAs, the frontier orbitals of the iso-PTA oligomers are delocalized along the entire carbon backbone, suggesting that pi-delocalization can extend through cross-linked carbon atoms. However, in contrast to the PTA oligomers, the bond lengths remain strictly constant and the reduction of the energy gap beyond the trimer is completely due to the correlation contribution. On the other hand, in the anions and cations, the bond lengths do change significantly with increasing chain length. Therefore, oxidation or reduction of the iso-PTA oligomer appears to switch on delocalization through cross-linked carbon atoms. Obviously, the effective conjugation length is specific and depends on the observable considered.     

High-performance liquid chromatography of in vitro synthesized poly(ADP-ribose) on ion-exchange columns, separation of oligomers of varying chain length and estimation of apparent branching

Separated macromolecular fractions of in vitro synthesized poly(ADP-ribose) by liver nuclei were subjected to ion-exchange chromatography in a programmed high-performance liquid chromatographic elution system. The effects of ionic strength, pH and temperature on the separation of poly(ADP-ribose) chains were determined. Short chain oligomers (up to n = 11) were fractionated into individual components by baseline separation. Each fraction was analyzed for chain length. Trace amounts of Ado(P)Rib(P)Rib(P) found in phosphodiesterase digests were taken as indication of apparent branching. In phosphodiesterase digests of the shorter oligomers, besides traces of the above component, two other digestion products were also observed, presumably representing oligomer termini, one terminal fragment being dominant in short oligomers. Medium and long chain oligomers were partly resolved to individual components, and especially the long oligomers exhibited marked temperature dependent elution patterns. Apparent branching increased with increasing chain length up to about 3% for n = 44 and components presumably indicating termini diminished to mere traces. The adenine spectra of all fractions identified individual components.     

Study of cross-conjugated iso-polytriacetylenes and related oligoenynes

Two series of monodisperse cross-conjugated oligomers based on enyne repeat units have been realized. The first class of molecules, iso-polytriacetylenes (iso-PTAs, 2), was divergently synthesized using an iterative sequence of palladium-catalyzed cross-coupling reactions of vinyl triflate 5 with terminal alkynes. The second series of oligoenynes (17-20) are based on an octatetrayne backbone, and result from homocoupling of the differentially protected iso-PTA oligomers 8-11. The longest member of this series, 20, spans ca. 5.6 nm from Si atom to Si atom and is composed of a contiguous sequence of 44 sp and sp(2) carbons. The lowest energy electronic absorption band for iso-PTA dimers in the progression 13 --> 9 --> 16 is consistently red-shifted as a result of extending the cross-conjugated structure. A similar comparison within each series (i.e., 16, 6-7, or 17-20), however, suggests little effect on the electronic characteristics of these molecules as oligomer length is increased. The solid-state properties of one derivative, 17, are also described.     

Poly(ethylene glycol)--oligolactates with monodisperse hydrophobic blocks: preparation, characterization, and behavior in water

Methoxypoly(ethylene glycol)-b-oligo-L-lactate (mPEG-b-OLA) diblock oligomers with monodisperse OLA blocks were obtained by fractionation of polydisperse block oligomers using preparative HPLC. The fractionated oligomers were composed of an mPEG block with a molecular weight of 350, 550, or 750 and an OLA block with a degree of polymerization of 4, 6, 8, or 10. The diblock oligomers with a low PEG content were fully amorphous, with glass transition temperatures ranging from -60 to -20 degrees C, indicating that the blocks were miscible. Upon heating aqueous dispersions of the block oligomers, cloud points, depending on the PEG/OLA ratio of the block oligomer, were observed at temperatures above 40 degrees C. The monodispersity of the hydrophobic block enabled the amphiphilic molecules to form nanoparticles in water with a hydrodynamic radius of 130-300 nm, at concentrations above the critical aggregation concentration (0.4-1 mg/mL), whereas polydisperse mPEG-b-OLAs gave formation of large aggregates. Static light scattering measurements showed that the nanoparticles have a low density (0.6-25 mg/mL), indicating that the particles are highly hydrated. In agreement herewith, the (1)H NMR spectra of nanoparticles in D2O closely resembled spectra in a good solvent for both blocks (CDCl3). It is therefore suggested that the nanoparticles contain a hydrated core of mPEG-b-OLA block oligomers, stabilized by a thin outer PEG layer. The particles were stable for two weeks, except for the mPEG350 series and mPEG750-b-OLA4, indicating that both the PEG block size and the PEG weight fraction of the oligomers determine their stability. The evident self-emulsifying properties of mPEG-b-oligo-l-lactates with monodisperse hydrophobic blocks as demonstrated in this study, together with their expected biocompatibility and biodegradability, make these systems well suitable for pharmaceutical applications.     

Side chain engineering and conjugation enhancement of benzodithiophene and phenanthrenequnioxaline based conjugated polymers for photovoltaic devices

A series of donor‐acceptor conjugated polymers incorporating benzodithiophene (BDT) as donor unit and phenanthrenequnioxaline as acceptor unit with different side chains have been designed and synthesized. For polymer P1 featuring the BDT unit and alkoxy chains substituted phenanthrenequnioxaline unit in the backbone, serious steric hindrance resulted in quite low molecular weight. The implementation of thiophene ring spacer in polymer P2 greatly suppressed the interannular twisting to extend the effective conjugation length and consequently gave rise to improved absorption property and device performance. In addition, utilizing the alkylthienyl side chains to replace the alkyl side chains at BDT unit in polymer P3 further enhanced the photovoltaic performance due to the increased conjugation length. For polymer P4, translating the alkoxy side chains at the phenanthrenequnioxaline ring into the alkyl side chains at thiophene linker group enhanced molecular planarity and strengthened π?π stacking. Consequently improved absorption property and increased hole mobility were achieved for polymer P4. Our results indicated that side chain engineering not only can influence the solubility of polymer but also can determine the polymer backbone planarity and hence the photovoltaic properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1915–1926     

Synthesis, structure, and nonlinear optical properties of cross-conjugated perphenylated iso-polydiacetylenes

Monodisperse, cross-conjugated perphenylated iso-polydiacetylene (iso-PDA) oligomers, ranging from monomer 15 to pentadecamer 25, have been synthesized by using a palladium-catalyzed cross-coupling protocol. Structural characteristics elucidated by X-ray crystallographic analysis demonstrate a non-planar backbone conformation for the oligomers due to the steric interactions between alkylidene phenyl groups. The electronic absorption spectra of the oligomers show a slight red-shift of the maximum absorption wavelength as the chain length increases from dimer 17 b to pentadecamer 25, a trend that has saturated by the stage of nonamer 22. Fluorescence spectroscopy confirms that the pendent phenyl groups present on the oligomer framework enhance emission, and the relative emission intensity consistently increases as a function of chain length n. The molecular third-order nonlinearities, gamma, for this oligomer series have been measured via differential optical Kerr effect (DOKE) detection and show a superlinear increase as a function of the oligomer chain length n. Molecular modeling and spectroscopic studies suggest that iso-PDA oligomers (n>7) adopt a coiled, helical conformation in solution.