AFM characterization of nanoscale ribbons grown from a series of oligo(p-phenyleneethynylene) derivatives

The key to optimizing the properties of molecular scale wires lies in understanding and controlling the solid-state morphologies. This paper examines the influence of oligomer chain length, solvent, and concentration on the formation of nanoscale ribbons on mica substrates from solutions of oligo(p-phenyleneethynylene)s (OPEs) with hexyloxy side chains and thioacetyl end groups. The OPEs are of different molecular chain lengths, in which the numbers ofp-dihexyloxyphenyleneethynylene repeat units, n, are 1, 3, 5, and 7, respectively, with their two ends capped with 4-thioacetylphenyl alligator groups. The atomic force microscope (AFM) is employed to investigate the thin film morphology and study the self-assembled organizations. Solvent and concentration are found to exert a strong influence on thin film morphology. Under suitable conditions, OPEs with 7 p-dihexyloxyphenyleneethynylene repeat units are driven to form micrometer-long nanoribbons, oriented preferably along the 3-fold symmetry axes of the mica substrate. The cross section of the nanoribbons is composed of 7 molecules as evaluated by AFM characterization. On the other hand, oligomers with shorter chain lengths (n = 1, 3, and 5) produce thin films featuring globular nanoaggregates, chains consisting of elongated grains, and rods, respectively. Plausible reasons for the variation in thin film morphology are discussed, based on the results obtained from investigation of oligomer chain length, solvent, and concentration effects. A subtle balance among molecular size and physicochemical properties of solute molecules, solvent molecules, and substrate is crucial for the formation of desired structures. Among them, oligomer chain length plays a key role in thin film morphology, and the critical number of repeat units in OPE/poly(p-phenyleneethynylene) molecules for the formation of nanoribbon structures with a molecular cross section is supposed to be 8 or 9.     

Effect of polymer chain length on membrane perturbation activity of cationic phenylene ethynylene oligomers and polymers

The interactions of poly(phenylene ethynylene)- (PPE-) based cationic conjugated polyelectrolytes (CPEs) and oligo(phenylene ethynylene)s (OPEs) with different model lipid membrane systems were investigated to gain insight into the relationship between molecular structure and membrane perturbation ability. The CPE and OPE compounds exhibit broad-spectrum antimicrobial activity, and cell walls and membranes are believed to be their main targets. To better understand how the size, in terms of the number of repeat units, of the CPEs and OPEs affects their membrane disruption activities, a series of PPE-based CPEs and OPEs were synthesized and studied. A number of photophysical techniques were used to investigate the interactions of CPEs and OPEs with model membranes, including unilamellar vesicles and lipid monolayers at the air/water interface. CPE- or OPE-induced dye leakage from vesicles reveals that the CPEs and OPEs selectively perturb model bacterial membranes and that their membrane perturbation abilities are highly dependent on molecular size. Consistent with dye-leakage assay results, the CPEs and OPEs also exhibit chain-length-dependent ability to insert into 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (DPPG) monolayers. Our results suggest that, for PPE-based CPE and OPE antimicrobials, chain length can be tuned to optimize their membrane perturbation ability.     

Superquenching in cyanine pendant poly(L-lysine) dyes: dependence on molecular weight, solvent, and aggregation.

A series of poly(L-lysines) ranging in number of repeat units (N(PRU)) from 6 to 900 has been synthesized and the photophysics of the series and monomer cyanine dye have been studied in solution. In water or aqueous dimethyl sulfoxide, the oligomers and polymers exhibit high sensitivity to fluorescence quenching by oppositely charged electron acceptors; in this study, 9,10-anthraquinone-2,6-disulfonate was used as a quencher for the cationic fluorescent polyelectrolytes. Quenching constants (K(SV)) measured in 50:50 (v/v) dimethyl sulfoxide-water increase monotonically with increase in N(PRU) ranging from 630 M(-1) for monomer to 1.2 x 10(9) M(-1) for dilute solutions of the polymer having N(PRU) approximately 900. The polymers having N(PRU) > 100 exhibit predominantly J-aggregate absorption and fluorescence and enhanced susceptibility to quenching. For the polymers exhibiting strong J-aggregation, the effective exciton domain quenched by a single quencher reaches approximately 100 PRU. The results of this study permit a semiquantitative analysis of superquenching of fluorescent polyelectrolytes in solution and the factors that control it.     

Synthesis, characterization, and application of cationic water-soluble oligofluorenes in DNA-hybridization detection

A simple and efficient approach was developed for the synthesis of a series of cationic water-soluble oligofluorenes up to a chain length of a heptamer. Bromoalkyl-substituted fluorenyl boronic esters as the key intermediates were synthesized by using a modified Miyaura reaction. With an increasing number of repeat units (trimer to hexamer), the size-specific oligomers have shown redshifts in both the absorption and emission maxima. The emission maximum reaches the limit for the hexamer in both water and buffer solution. The quantum yields of the oligomers decreased with increased oligomer size in water. Both fluorescence quenching of the oligomers by 9,10-anthraquinone-2,6-disulfonate and the fluorescence resonance energy transfer experiments with the oligomers as the donor and fluorescein (Fl)-labeled double-stranded DNA (dsDNA-Fl) as the acceptor revealed the chain-length-dependent behavior. The Stern-Volmer quenching constant increased with the molecular size, whereas the highest donor-sensitized Fl emission was observed for the hexamer. These size-specific oligomers also served as a model to study the structure-property relationships for cationic polyfluorenes.     

Oligo(p‐phenylene‐ethynylene)‐Derived Super‐π‐Gelators with Tunable Emission and Self‐Assembled Polymorphic Structures

Linear π‐conjugated oligomers are known to form organogels through noncovalent interactions. Herein, we report the effect of π‐repeat units on the gelation and morphological properties of three different oligo(p‐phenylene‐ethynylene)s: OPE3 , OPE5 , and OPE7 . All of these molecules form fluorescent gels in nonpolar solvents at low critical gel concentrations, thereby resulting in a blue gel for OPE3 , a green gel for OPE5 , and a greenish yellow gel for OPE7 . The molecule–molecule and molecule–substrate interactions in these OPEs are strongly influenced by the conjugation length of the molecules. Silicon wafer suppresses substrate–molecule interactions whereas a mica surface facilitates such interactions. At lower concentrations, OPE3 formed vesicular assemblies and OPE5 gave entangled fibers, whereas OPE7 resulted in spiral assemblies on a mica surface. At higher concentrations, OPE3 and OPE5 resulted in super‐bundles of fibers and flowerlike short‐fiber agglomerates when different conditions were applied. The number of polymorphic structures increases on increasing the conjugation length, as seen in the case of OPE7 with n=5, which resulted in a variety of exotic structures, the formation of which could be controlled by varying the substrate, concentration, and humidity.     

Synthesis, Characterization and Properties of Novel Star-Shaped π-Conjugated Oligomers with Triphenylamine Core

Four new star‐shaped π‐conjugated oligomers ( TPA‐CZ3 , TPA‐TPA3 , TPA‐PTZ3 and TPA‐BT3 ) with triphenylamine as a core and different electron‐donating ability groups, carbazole, triphenylamine, phenothiazine and bithiophene, as peripheral units have been designed and synthesized via the Heck reaction. These oligomers show good solubility in common organic solvents. Their photophysical, electrochemical, electronic structure and charge transfer properties between these star‐shaped π‐conjugated oligomers and N,N′‐bis(1‐ethylpropyl)‐3,4:9,10‐perylene bis(tetracarboxyl diimide) (EP‐PDI) have been investigated by UV‐vis absorption spectra, photoluminescence (PL) spectra, cyclic voltammetry (CV) measurement, theoretical calculations and fluorescence quenching. The results show that the absorptions and fluorescences of TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 are red shifted with the electron‐donating ability of the peripheral unit increasing from carbazole to triphenylamine and phenothiazine. In addition, although the bithiophene group has a weaker electron‐donating ability than carbazole, triphenylamine and phenothiazine, the absorption and fluorescence of TPA‐BT3 have a red shift than those of TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 because TPA‐BT3 has a longer conjugation length than TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 . The triphenylamine core and the peripheral units can constitute a large conjugated structure. The fluorescence quenching properties indicate that efficient charge transfer can happen between the star‐shaped oligomers and EP‐PDI.     

Polarons, bipolarons, and side-by-side polarons in reduction of oligofluorenes

The nature of charge carriers in conjugated polymers was elucidated through optical spectroscopy following single- and multielectron reduction of 2,7-(9,9-dihexylfluorene) oligomers, F(n), n = 1-10, yielding spectra with the two bands typical of polarons upon single reduction. For short oligomers addition of a second electron gave a single band demonstrating the classic polaron-bipolaron transition. However, for long oligomers double reductions yielded spectra with two bands, better described as two polarons, possibly residing side-by-side in the F(n) chains. The singly reduced anions do not appear to delocalize over the entire length of the longer conjugated systems; instead they are polarons occupying approximately four fluorene repeat units. The polarons of F(3) and F(4) display sharp absorption bands, but for longer oligomers the bands broaden, possibly due to fluctuations of the lengths of these unconfined polarons. DFT calculations with long-range-corrected functionals were fully consistent with the experiments describing polarons in anions, bipolarons in dianions of short oligomers, and side-by-side polarons in dianions of long oligomers, while results from standard functionals were not compatible with the experimental results. The computations found F(10)(2-), for example, to be an open-shell singlet ( ≈ 1), with electrons in two side-by-side orbitals, while dianions of shorter oligomers experienced a gradual transition to bipolarons with states of intermediate character at intermediate lengths. The energies and extinction coefficients of each anionic species were measured by ultraviolet-visible-near-infrared absorption spectroscopy with chemical reduction and pulse radiolysis. Reduction potentials determined from equilibria mirrored oxidation potentials reported by Chi and Wegner. Anions of oligomers four or more units in length contained vestigial neutral (VN) absorption bands that arise from neutral parts of the chain. Energies of the VN bands correspond to those of oligomers shorter by four units.     

Second hyperpolarizability of ethynyl-linked azobenzene molecular wires

A series of oligomers consisting of ethynyl-linked azobenzene units was prepared using Pd-catalyzed cross coupling. The linear and nonlinear optical properties of the oligomers were investigated. The molecular second hyperpolarizability, gamma, followed the power law gamma proportional, variant n(2.12+/-0.05) (n is the number of repeat units) for unusually large molecular lengths exceeding 360 conjugated bonds (>49 nm). The exceptional exciton delocalization length is attributed to the rigidity of the conjugated backbone.     

Nonlinear Optical Properties of D-π-A-π-D Type Oligomers with Different Conjugation Length

The conjugation length-dependent nonlinear optical properties of fluorenone-based linear conjugated oligomers have been investigated by experimental and theoretical methods. In-frared spectra and the steady-state absorption spectra show that the increase of conjugated unit could enhance the stretching vibration peaks of C=C and lead to a red-shift of the absorption peaks. Meanwhile, the two-photon fluorescence (TPF) intensity is gradually en-hanced with the increase of excitation energy, and the TPF effciency is obviously higher after the introduction of fluorene-ethylene units. The sum-over-states approach was used to model the two-photon absorption (TPA) cross-sections of oligomers, and the theoretical values agree well with the experimental data obtained from the femtosecond open-aperture z-scan technique. The results exhibit that the extension of conjugated system indeed plays a role in the improvement of TPA behavior of oligomers.     

A Portrait of the OPE as a Biological Agent

Oligophenylene ethynylenes, known as OPEs, are a sequence of aromatic rings linked by triple bonds, the properties of which can be modulated by varying the length of the rigid main chain or/and the nature and position of the substituents on the aromatic units. They are luminescent molecules with high quantum yields and can be designed to enter a cell and act as antimicrobial and antiviral compounds, as biocompatible fluorescent probes directed towards target organelles in living cells, as labelling agents, as selective sensors for the detection of fibrillar and prefibrillar amyloid in the proteic field and in a fluorescence turn-on system for the detection of saccharides, as photosensitizers in photodynamic therapy (due to their capacity to highly induce toxicity after light activation), and as drug delivery systems. The antibacterial properties of OPEs have been the most studied against very popular and resistant pathogens, and in this paper the achievements of these studies are reviewed, together with almost all the other roles held by such oligomers. In the recent decade, their antifungal and antiviral effects have attracted the attention of researchers who believe OPEs to be possible biocides of the future. The review describes, for instance, the preliminary results obtained with OPEs against severe acute respiratory syndrome coronavirus 2, the virus responsible for the COVID-19 pandemic.     

Theoretical study of vibrational and optical spectra of methylene-bridged oligofluorenes

We report a systematic characterization of methylene-bridged fluorene oligomers constructed of two, four, six, and eight aromatic rings using time-dependent density functional theory (TDDFT), the ab initio approximate coupled-cluster singles and doubles (CC2) method, and semiempirical spectroscopic Zerner's intermediate neglect of differential overlap method (ZINDO/S). Geometry optimizations have been performed for the ground state and for the first electronically excited state. Vertical excitations and the fluorescence transition from the lowest excited state have been calculated. Computed ground-state geometries and infrared spectra for fluorene are in good agreement with experimental results. The RI-CC2 and ZINDO/S absorption and fluorescence spectra agree very well with the available experimental data for studied fluorene oligomers and for para oligophenylenes films. On the other hand, TDDFT calculations underestimate excitation and fluorescence energies systematically for larger systems (N > 4) in comparison with the above-mentioned results. The effective conjugation length was estimated to 13-14 repeat units. The computed radiative lifetimes for the fluorene molecule show good agreement with experiment within realistic expectations. The decrease of the radiatiave fluorescence lifetime with the increase in the conjugation length has been discussed also.     

On the conjugation length for oligo(ethynylnaphthalene)-based molecular rods

The synthesis is described for a small series of oligomers built from (2, 3, 4 or 6) ethynyl-naphthalene repeat units and end-capped with solubilising 1,2,3-tris-dodecyloxy-benzene groups. These compounds absorb in the near-UV region and exhibit strong fluorescence in both fluid solution and a glassy matrix at 77 K. The spectral profiles are fully consistent with a structurally heterogeneous ground state becoming more planar upon excitation and with the low-temperature glass further stabilising the co-planar orientation. The absorption and fluorescence maxima move towards lower energy with increasing number of repeat units and there is a corresponding increase in the Huang-Rhys factor for the radiative process. The non-radiative rate constants also depend on molecular length and are well explained in terms of the energy-gap law. In contrast, very weak phosphorescence is observed at 77 K for which the peak maximum and lifetime remain insensitive to the number of naphthalene units. The triplet lifetimes recorded at ambient temperature are also independent of the molecular length but the triplet-triplet absorption spectra change throughout the series. These results are discussed in terms of the degree of electronic coupling between adjacent repeat units for each of the relevant excited states. During these studies it was noted that the rate of intersystem crossing to the triplet manifold is but weakly affected by heavy-atom perturbers. A non-fluorescent complex is formed between iodoethane and the molecular rod but the corresponding bimolecular process occurs at well below the diffusion-controlled limit. This behaviour is considered in terms of spin-orbit coupling between the excited states and takes account of the differing conjugation lengths.     

Oligomers of hexa-peri-hexabenzocoronenes as "super-oligophenylenes": synthesis, electronic properties, and self-assembly

Hexa-peri-hexabenzocoronene (HBC) is a remarkable polycyclic aromatic hydrocarbon and is often called "superbenzene" because of its similarity to benzene. In this article we present the facile synthesis of oligomers of HBC, up to trimers (3, 4, 5a-c) with different modes of connection. UV-vis and fluorescence spectroscopy studies reveal that the oligomers are electronically decoupled. This arises from the small atomic orbital coefficients of the bridge-head carbon atoms, the large torsion angle between the HBC units, and the large distance of interacting transition dipoles due to the size of the HBC chromophore. For comparison, a methylene-bridged HBC dimer 6, so-called "superfluorene", was prepared. The induced planarity improves pi-conjugation and suppresses the geometrical relaxation of the backbone upon electronic excitation, leading to a prominent 0-0 transition band in the fluorescence spectra. The self-assembly of the oligomers and of superfluorene 6 was studied by wide-angle X-ray diffraction (WAXD) in the bulk state, and ordered columnar stacking occurs in the HBC dimer 3, p-HBC trimer 4, and superfluorene 6. Measurements of shear-aligned samples show that, despite increasing aspects ratio by linear entrainment of disks, the anitropic element that is subject to alignment by shear is the supramolecular columns.     

Poly(DMI-1, 2-Diazinediylethene-l, 2-Diols)

Oligomers of 2 to 9 units having a diazinediylethene-1, 2-diol repeating unit have been prepared by a cyanide ion-catalyzed self-condensation of pyridazine-3, 6-, pyrazine-2, 5-, or pyrimidine-4, 6-dialdehyde. These are the first known representatives of a class of conjugated polymeric enediol materials derivable specifically from these three structurally related diazine dialdehydes. The oligomers, isolated as their potassium salts, are soluble in acid and base with an isoelectric point at pH 6.5. In base, they give dark red-brown solutions whose color, attributable to their semidione ion radical form, is rapidly discharged by oxygen (air) or by the addition of ferric ion, which gives an immediate precipitation of the black chelate. Of several possible methods evaluated for the preparation of the free dialdehydes, only that involving ozonization of the distyryldiazines was found to be of preparative value.     

Retention mechanism, isocratic and gradient-elution separation and characterization of (co)polymers in normal-phase and reversed-phase high-performance liquid chromatography

Synthetic (co)polymers or (co)oligomers with two (or more) repeating groups show not only molar mass distribution, but also composition and sequence distribution of the individual repeat units. To characterize such two- (or more-) dimensional distribution, liquid chromatography under "critical conditions" has been suggested, where the separation according to one type of repeating units is suppressed by balancing the adsorption and the size-exclusion effects. In present work it is shown that by combination of adequately selected separation conditions in normal-phase and in reversed-phase systems, the two-dimensional distribution mode can be adjusted to result in the separation following the distribution of any of the two repeat units in ethylene oxide-propylene oxide block (co)oligomers. Based on the retention mechanism suggested, prediction and optimization of the conditions for isocratic and gradient-elution separations of (co)oligomers is possible. HPLC-MS with atmospheric-pressure chemical ionization is a valuable tool for unambiguous identification of the individual (co)oligomers and their tracking in course of method development. Gradient elution can be used for the separation and characterization of block (co)oligomers of ethylene oxide (EO) and propylene oxide (PO) according to the number of the units in one block, while the separation according to the distribution of the units in the other block is suppressed. The effects of the arrangement of the individual EO and PO blocks in the block (co)oligomers (the sequence distribution) affects significantly the retention behavior and the selection of the optimum separation conditions.     

m-Phenylene ethynylene sequences joined by imine linkages: dynamic covalent oligomers

Imine metathesis between m-phenylene ethynylene oligomers of various lengths was performed in acetonitrile, a solvent in which oligomers containing eight or more repeat units adopt a compact helical conformation. The equilibrium constants and corresponding free energy change for the imine metathesis reactions were estimated. The results showed that the magnitude of equilibrium shifting measured by the free energy change for the formation of imine-containing oligomers increases linearly below a critical product chain length and grows asymptotically above it. The linear region is ascribed to the constant increase in contact area between monomer units of adjacent helical turns as the product chain grows to the 12-mer. Once the ligation product is 12 units in length, full contact is made between adjacent helical turns. On the other hand, for imine metathesis between oligomers leading to products having more than 12 units, the driving force is the difference between the folding energy of products and that of reactants. The additional stabilizing energy is roughly constant, regardless of the chain length, since the contact area between adjacent helical turns is unchanged. Consistent with the notion that the imine bond only minimally destabilizes the helical conformation, the position of the imine bond in the ligation product has been observed to have no significant effect on the folding stability. The magnitudes of equilibrium shifting are similar for ligation products of the same length but having the imine at various positions along the sequence. This suggests that the imine bond is compatible with the m-phenylene ethynylene backbone, regardless of the position in the sequence. Imine metathesis of m-phenylene ethynylene oligomers could allow a quick access to an unbiased, dynamic library of oligomer sequences joined by imine linkages.     

Sudden, "step" electron capture by conjugated polymers

Data showing significant time-resolution-limited "step" capture of electrons following radiolysis by 7 - 10 ps electron pulses in a series of different length and different concentration conjugated polyfluorene polymers in tetrahydrofuran (THF) are presented. At the highest concentration, ～48 mM in repeat units for lengths from 20 to 133 fluorenes, ～30% of the electrons formed during pulse radiolysis were captured in the step, with a constant efficiency per repeat unit. Step capture per repeat unit (q = 6.9 M(-1)) is 60% of the presolvated electron capture efficiency previously reported for biphenyl in THF, giving capture per polymer molecule 12-80 times larger than that for biphenyl at the same concentration. This increase in capture efficiency is large compared to the rate constant per repeat unit for diffusion-limited electron attachment to the same molecules, which is 13% of that of a single unit of fluorene. Plausible mechanisms of this fast capture are explored. It is shown that both capture of quasi-free and localized presolvated electrons can adequately explain the observations. The large yield of radical anions at low concentration of polyfluorene enables observation of subsequent chemistry on the picosecond time scale in these systems, which would otherwise been limited by diffusional attachment to the nanosecond regime.     

The effect of 2,2-dicyanovinyl groups as electron acceptors in push-pull substituted oligo(1,4-phenylenevinylene)s

The newly synthesized oligo(1,4-phenylenevinylene) series 2a-d with bis(2-hexyloctyl)amino groups as electron donors and 2,2-dicyanovinyl groups as electron acceptors represents conjugated oligomers with strong push-pull effects. Due to the decrease of the intramolecular charge transfer with increasing numbers of repeat units (n=1-4), the long-wavelength transition shows a particularly great hypsochromic shift for the extension of the chromophore.     

Molecular structure and electronic properties of a series of oligoalkylthiophenes: A theoretical investigation

Molecular geometries and electronic properties of 3-alkylthiophenes (ATs) and their oligomers (OATs) are studied by the density functional theory (DFT). Calculations are performed on the oligomers formed by n repeating units, where n ranges from 1 to 6, using the B3LYP/6-31G** level of theory. The results obtained show that the doped oligomers have more satisfactory structural and electronic characteristics for the conducting polymers. The conjugated system in the doped oligomers has more aromaticity, with expanded and planar chains. The calculated energy gap values between the frontal orbitals and also the ionization potential values for the oligomers indicate that with increase in the oligomer chain length, the conductive band gap decreases. Furthermore, our calculations suggest that an electron-donating alkyl substituent at position 3 of the thiophene ring plays an important role in the structural and electronic properties of the polymers.     

Surface modification of waterborne polyurethane

Fluorinated urethane oligomers (SMAs) having repeat unit identical to the hard segment of base polyurethane (PU) have been synthesized and blended with base PU prior to dispersion. XPS and static contact angle measurements showed that surfaces of dispersion cast film are significantly enriched with SMA although SMA and base PU were miscible in bulk phase showing a single glass transition temperature. AFM showed that surface roughness of the dispersion cast film increased over 13 times with the addition of SMA (15%) providing possible mechanism of increased water and oil resistance as well as low friction coefficient of the film.