Oligo Phenylenevinylene Research Articles

Exploring Electronic and Conformational Attributes of an Organic Donor‐Bridge‐Acceptor Molecular System

AbstractThis research explores the electronic properties and conformational dynamics of the ZnP‐COPV‐ (Zinc Porphyrin ‐ Carbon bridged Oligo Phenylenevinylene ‐ Fullerene) organic semiconductor via specialized Density Functional Theory (DFT) and Molecular Dynamics (MD) computational techniques. First, through DFT calculations, essential HOMO (Highest Occupied Molecular Orbital), LUMO (Lowest Unoccupied Molecular Orbital), and Molecular Electrostatic Potential (MEP) electronic attributes are meticulously dissected providing insights into the intricate charge transfer processes between the constituent donor‐acceptor moieties. Furthermore, MD simulations are employed to unveil the molecular system's multifaceted conformational flexibility and stability. The Root‐mean‐squared deviation (RMSD), end‐to‐end distance, and torsional angles quantitative analysis of conformational attributes support the carbon‐bridged oligo‐phenylenevinylene (COPV) molecular wire's ‐skeleton planar and rigid conformation. This minimal end‐to‐end distance variation (within Å) compared to the initially extended structure and the constrained torsional motion (within for ZnP‐COPV and for COPV‐) after thermalization showcases COPV's ability to maintain structural rigidity over time, aligning with the concept of effective ‐conjugation. Finally, through the lens of time dependent (TD)‐DFT, the dynamic evolution of the HOMO–LUMO energy gap, TD‐DFT excitation energies and oscillator strengths are explored as the molecular structure transforms over time. The observed energy gap variation underscores the molecule's adaptability in the face of structural modifications, hinting at an intriguing connection between structural stability and enhanced electronic properties. The research provides a comprehensive understanding of the intricate interplay between conformational dynamics and electronic attributes in organic semiconductors, providing quantitative insights crucial for designing stable, high‐performance materials for cutting‐edge optoelectronic applications and helping advance the collective understanding of sustainable energy conversion.

Some Remarkable Rheological and Conducting Properties of Hybrid PVC Thermoreversible Gels/Organogels.

We report on investigations into the rheological properties of organogels prepared from triarylamine trisamide (TATA) and oligo phenylene vinylene (OPVOH) molecules in binary organogel gels and in ternary thermoreversible networks with poly vinyl chloride (PVC). In the case of OPVOH, we show that the modulus of the ternary gel is simply the sum of the modulus of each binary gel, corresponding to the so-called Voigt upper limit. In contrast, TATA/PVC ternary gels generally exceed the Voigt upper limit. In an attempt to account for this unexpected outcome, we hypothesized that a de-solvation process might occur in the PVC fibrils that possibly originates in the propensity of TATA molecules to form molecular compounds with the solvent. Finally, the conducting properties of TATA/solvent organogels and TAT/PVC/solvent reversible networks were measured. It was found that they strongly depend on the solvent type but are not significantly altered when PVC is present. Therefore, PVC gels can be made conducive by incorporating TATA fibers.

Modeling of molecular ternary logic gates and circuits based on diode structures

Modeling in molecular electronics is of great importance, and the use of semiconductor components for this type of modeling accelerates the development process in this field. In this work, a typical circuit model is proposed for modeling molecular components. Accordingly, an asymmetric oligo-phenylene vinylene (OPV) molecular diode and a bipyridine-biborinine molecular diode are modeled. A good agreement is observed between the current curves from the proposed circuit models and the atomic simulations of the molecules. Additionally, the electron density, the distribution of molecular orbitals, and the potential drop profile at + 1 and - 1V are obtained and analyzed for the bipyridine-biborinine molecular diode using the density functional theory (DFT) in combination with the non-equilibrium Green's function (NEGF). Using different molecular gates and circuits based on the molecular devices, we have modeled the ternary NOT logic gate, ternary NOR logic gate, ternary NAND logic gate, negative ternary inverter (NTI) logic gate, positive ternary inverter (PTI) logic gate, ternary buffer, ternary decoder, and ternary half adder.

Electron n-doping of a highly electron-deficient chlorinated benzodifurandione-based oligophenylene vinylene polymer using benzyl viologen radical cations

Successful electron-doping of highly electron-deficient chlorinated benzodifurandione-based polyphenylene vinylene using viologen radical cation.

Electrosynthesis and characterization of a new semi-conducting oligomer deriving from a disubstituted chalcone: 4-dimethylamino -4′-methoxychalcone

An oligo phenylene vinylene was electrosynthesized by the anodic oxidation of the 4-dimethylamino-4′-methoxychalcone (DMAMC) at a constant potential in nitromethane on a platinum electrode. 1H and 13C NMR, FTIR and UV spectroscopy, confirmed the chemical structure of the obtained oligomer. In addition, the latter was thermally stable up to 190 °C and exhibited two emission peaks in the yellow-orange zone. The values of the corresponding optical and electrochemical band gaps were found to be 2.04 and 1.68 eV, respectively. Finally, a mechanism for the electro-oligomerization of DMAMC was proposed based on the experimental study and a theoretical modelisation using DFT calculation.

The oligomer approach: An effective strategy to assess phenylene vinylene systems as organic heterogeneous photocatalysts in the degradation of aqueous indigo carmine dye

Four oligo-phenylenevinylenes (OPVs) were synthesized by the Mizoroki-Heck cross-coupling reaction to provide a deeper understanding of the mechanism and fate of phenylenevinylene systems when applied to the heterogeneous photocatalytic degradation of indigo carmine (IC) dye in aqueous media. OPVs displayed visible light absorption near 500 nm and appreciable emission properties. The stability, mechanism, and photodegradation activity of the OPV systems over aqueous indigo carmine were investigated using radical scavengers, a singlet oxygen (1O2) trap, and ESI-IT-MS. It was confirmed that superoxide radical (O2·−), 1O2, and direct oxidation are responsible for dye degradation. Hydroxide radical formation, under neutral pH conditions, does not occur, and it was corroborated by the HOMO and LUMO levels of the photocatalysts. Additionally, the use of oxalic acid as an electron sacrificial donor was demonstrated as an effective approach to enhance the OPVs photocatalytic activity. However, a significant decrease in activity during the first three irradiation cycles was observed, indicating that the enhancement in photo- and chemical stability is required for further dye-contaminated water treatment applications.

Effect of the End Groups and the Solvent on the Gelation of the Hybrid Materials from Poly (Vinyl Chloride) (PVC) and Oligo Phenylene Vinylene (OPV)

The role of the end-groups of three oligophenylene vinylene (OPV) and the solvents on the hybrid materials from poly (vinyl chloride) (PVC) and the OPV are examined. The gelation of the three organogel OPVs and of the hybrid materials in bromobenzene and benzyl alcohol was characterized. The morphology, as well as the thermodynamic properties, of these OPV and hybrid materials showed that they depended mostly on the solvent and very little on the different end-groups located on the OPV backbones.

Exploring the nitro group reduction in low-solubility oligo-phenylenevinylene systems: Rapid synthesis of amino derivatives

A small series of amino oligo-phenylenevinylenes (OPVs) were successfully synthesized from their nitro-analogs in a rapid, simple, and highly efficient fashion employing a sodium sulfide/pyridine system as a reducing agent. In this research, classic and sustainable reduction methodologies including NH4HCO2/Zn and a choline chloride/tin (II) chloride deep eutectic solvent (DES) were also evaluated, showing degradation products, incomplete reactivity, and product isolation difficulties in all cases. The straightforward Na2S/pyridine synthetic protocol proved to maintain the E-E stereochemistry of the OPV backbone that has been previously assembled by the Mizoroki–Heck cross-coupling reaction. Also, the optoelectronic properties were determined and discussed, considering the amino group insertion in these conjugated systems as a contribution for future construction of novel materials with applications in supramolecular electronics, light harvesting, and photocatalysis.

Macromolecular Effect Stabilized Color-Tunable and Room Temperature Charge-Transfer Complexes Based on Donor–Acceptor Assemblies

We report one of the first examples of room temperature stable solid-state charge transfer (CT) complexes based on a segmented π-conjugated polymer and rylene diimide donor–acceptor system having tunable optical transitions from the visible to NIR region in the solar spectrum. Semicrystalline and amorphous segmented oligo-phenylenevinylene (OPV) chromophore containing polymers were tailor-made with flexible polymethylene chains in the backbone. The electron rich segmented OPV polymers were complexed with two electron-deficient diimides based on naphthalene (NDI) and phenylene (PDI) core. The binary complexes of segmented OPV polymers and rylene diimides produced unique classes of CT complexes based on OPV-NDI and OPV-PDI chromophore diads. Electron microscope, polarizing microscope, and X-ray diffraction analyses provided direct evidence for the two-dimensional lamellar packing of D–A self-assembly in the solid state. Detailed absorption and emission photophysical studies revealed that the donor OPV polymers and acceptor chromophores exhibited a 1:1 complex with respect to the long-range order of D–A–D–A–D–A π-stacked supramolecular assemblies. The role of the macromolecular effect on the CT complexation was further investigated using structurally identical OPV monomers. The monomer OPV-NDI complexes (or PDI complexes) were found to exhibit CT complex in the solution; however, they underwent uncontrollable phase separation into their individual D and A crystalline domains and lost their CT self-assembly in the solid state. Interestingly, the macromolecular effect driven supramolecular self-organization of long chain segmented OPV polymers produced stable CT complexes both in solution and solid state under ambient conditions. Segmented OPV polymer + PDI and segmented OPV polymer + NDI complexes were produced as red and green colored CT complexes, respectively. This enabled the accomplishment of room temperature stable CT complexes in π-conjugated polymers having absorption ranging from 350 to 1100 nm. These donor–acceptor CT self-assemblies are processable into thin films under solvent free melt crystallization process; thus, the present segmented polymer design strategy opens up a platform for donor–acceptor CT complexes.

Synthesis of Rod-coil Molecules bearing Oligo-Phenylene Vinylene Motifs: Effect of PEO Chain Lengths on the Evolution of Nanostructures Morphology and their Photophysical Properties

The applications of nano-dispersed organic conjugated active compounds or materials as well as current research is concerned mainly with optimization and control of the optical properties, by particle size and supramolecular structure of the particles. The aromatic macromolecules consisting of conjugated rigid rod segment and hydrophilic flexible chain as coil in aqueous solution can aggregate into a variety of supramolecular structures through mutual interaction between aromatic rod and hydrophilic chains of molecules and water. Here we report the synthesis of newer oligo phenylene vinylene (OPV) based rod-coil molecules with varying chain-length polyethylene oxide (PEO) repeating units (n = 8, 17, 45). Formation and photophysical properties of their nanostructures in water are studied comparatively. The nanostructures evolution of these molecules is observed with simple reprecipitation method. The stable nanostructures were formed without addition of any surfactants. The fabricated nanostructures ultimately give the materials with ‘controlled’ aggregation induced enhanced photophysical properties. The self-assembly of such OPV type rod molecules in water without adding any surfactants, therefore, can provide a strategy for the construction of well-defined and stable nanostructures with certain chemical functionalities and physical properties as advanced materials for photonic, electronic and biological applications. Copyright © VBRI Press.

Chemistry: A Bridge between Molecular World and Real World

This essay summarizes a personal history of studies on fluoride-mediated reactions of enol silyl ethers, metal homoenolate, cytochalasin and cortisone synthesis, cycloaddition chemistry of cyclopropenone acetals and dipolar trimethylenemethanes, biological activity of organofullerenes and DNA and siRNA delivery, organocuprate(I) reaction mechanisms, iron-catalyzed cross coupling and C-H activation reactions, 15O labeling for positron emission tomography (PET), functional fullerene molecules including bucky ferrocene, shuttlecock molecules and [10]cyclophenacene, fullerene bilayer vesicles, new design materials for organic and lead perovskite solar-cell fabrication, carbon-bridged oligophenylene vinylenes and single-molecule atomic-resolution real-time transmission electron microscopy (SMART-EM) for structural and kinetic studies of molecules and molecular clusters. It also describes how the encounters with key people may change the course of your scientific research as well as of your personal life. These examples suggest that life is a stochastic process, and, moreover, science in the future would be something that we do not even imagine now as a subject of research.

Unusual alignment during wet coating of oligo(phenylene vinylene)s thin films

Were formed anisotropic thin films of oligo(p-phenylene vinylene) dye on the surface of rubbed nylon during rod-coating from chloroform and chlorobenzene solutions. The order parameter and alignment direction of films depend on the solvent type and the temperature. On coating from chloroform solution molecules in the dye film align perpendicular and parallel to rubbing direction at temperatures below 40 °C and above 60 °C, correspondingly. Homogeneously oriented anisotropic films with a dichroic ratio of more than 25 were obtained.

Ultralong 20 Milliseconds Charge Separation Lifetime for Photoilluminated Oligophenylenevinylene–Azafullerene Systems

AbstractThe synthesis and characterization of oligophenylenevinylene (OPV)–azafullerene (C59N) systems in the form of OPV–C59N donor–acceptor dyad 1 and C59N–OPV–C59N acceptor–donor–acceptor triad 2 is accomplished. Photoinduced electronic interactions between OPV and C59N within 1 and 2 are assessed by UV–vis and photoluminescence. The redox properties of 1 and 2 are investigated, revealing a set of one‐electron oxidation and three one‐electron reduction processes owed to OPV and C59N, respectively. The electrochemical bandgap for 1 and 2 is calculated as 1.44 and 1.53 eV, respectively, and the free energy for the formation of the charge‐separated state for 1 and 2 via the singlet‐excited state of OPV is found negative, proving a thermodynamically favorable the process. Photoexcitation assays are performed in toluene and o‐dichlorobenzene (oDCB) and the reactions are monitored with time‐resolved absorption and emission spectroscopies. Competitive photoinduced energy and electron transfer are identified to occur in both systems, with the former being dominant in 2. Markedly, the charge‐separated state in oDCB exhibits a much longer lifetime compared to that in toluene, reaching 20 ms for 1, the highest ever reported value for fullerene‐based materials. These unprecedented results are rationalized by considering conformational phenomena affecting the charge‐separated state.

A Chiral Recognition System Orchestrated by Self‐Assembly: Molecular Chirality, Self‐Assembly Morphology, and Fluorescence Response

AbstractThe newly developed oligophenylenevinylene (OPV)‐based fluorescent (FL) chiral chemosensor (OPV‐Me) for the representative enantiomeric guest, 1,2‐cyclohexanedicarboxylic acid (1,2‐CHDA: RR‐ and SS‐form) showed the high chiral discrimination ability, resulting in the different aggregation modes of OPV‐Me self‐assembly: RR‐CHDA directed the fibrous supramolecular aggregate, whereas SS‐CHDA directed the finite aggregate. The consequent FL intensity toward RR‐CHDA was up to 30 times larger than that toward SS‐CHDA. Accordingly, highly enantioselective recognition was achieved. Application to the chirality sensing was also possible: OPV‐Me exhibited a linear relationship between the FL intensity and the enantiomeric excess through the morphological development of stereocomplex aggregates. These results clearly show that the chiral recognition ability is manifested by the amplification cascade of the chirality difference through self‐assembly.

A Chiral Recognition System Orchestrated by Self-Assembly: Molecular Chirality, Self-Assembly Morphology, and Fluorescence Response.

The newly developed oligophenylenevinylene (OPV)-based fluorescent (FL) chiral chemosensor (OPV-Me) for the representative enantiomeric guest, 1,2-cyclohexanedicarboxylic acid (1,2-CHDA: RR- and SS-form) showed the high chiral discrimination ability, resulting in the different aggregation modes of OPV-Me self-assembly: RR-CHDA directed the fibrous supramolecular aggregate, whereas SS-CHDA directed the finite aggregate. The consequent FL intensity toward RR-CHDA was up to 30 times larger than that toward SS-CHDA. Accordingly, highly enantioselective recognition was achieved. Application to the chirality sensing was also possible: OPV-Me exhibited a linear relationship between the FL intensity and the enantiomeric excess through the morphological development of stereocomplex aggregates. These results clearly show that the chiral recognition ability is manifested by the amplification cascade of the chirality difference through self-assembly.

Fluorescent-Tagged Biodegradable Polycaprolactone Block Copolymer FRET Probe for Intracellular Bioimaging in Cancer Cells.

The present investigation reports a new fluorophore-tagged biodegradable polycaprolactone (PCL) block copolymer FRET-probe for intracellular imaging in cancer therapy. A hydroxyl functionalized π-conjugated oligo-phenylenevinylene (OPV) chromophore was tailor-made, and it was incorporated in a t-butyl ester substituted polycaprolactone block copolymer via ring opening polymerization. This blue-luminescent OPV-PCL triblock self-assembled as <200 nm spherical nanoparticles (FRET donor), and it encapsulated water insoluble Nile red (NR, FRET acceptor) to yield an OPV-NR FRET probe. Selective photo excitation of the OPV chromophore in block nanoassemblies enabled the excitation energy transfer from the OPV to NR and facilitated the efficient FRET process in aqueous medium. Time-correlated fluorescent decay dynamics and detailed photophysical studies were carried out to estimate the Förster distance, donor-acceptor distance, and the excitation energy transfer efficiency. These parameters confirmed the occurrence of the FRET process within the confined nanoparticle environment. The PCL chains in the FRET probe were susceptible to enzymatic biodegradation in intracellular environments, and the degradation process controlled the FRET on/off mechanism. Cytotoxicity studies revealed that the FRET probe was biocompatible and nontoxic to cells, and the FRET-probe was found to be readily taken up by the cancer cells, and it was internalized in the cytoplasm and peri-nuclear environment. Selective photoexcitation of the OPV chromophore in a confocal microscope exhibited dual emission from the FRET probe. The cancer cells exhibited blue luminescence (self-emission) with respect to the OPV chromophore (in the blue channel) and bright red-luminescence from the NR dye followed by the FRET process at the cellular level (in the red channel). The dual luminescence characteristics, biodegradation and biocompatibility, make the newly designed PCL-OPV-NR FRET probe an excellent biomedical nanodevice for bioimaging applications, and the proof-of-concept was established in cervical (HeLa) and breast cancer (MCF 7) cell lines.

π-Conjugate Fluorophore-Tagged and Enzyme-Responsive l-Amino Acid Polymer Nanocarrier and Their Color-Tunable Intracellular FRET Probe in Cancer Cells.

The present investigation accounts one of the first example of enzyme-responsive and π-conjugate-tagged l-amino acid amphiphilic polymer and their fluorescence resonance energy transfer (FRET) probes for color-tunable intracellular bioimaging in cancer cells. Melt polymerizable oligo-phenylenevinylene (OPV) π-conjugated diol was tailor-made and subjected to thermo-selective melt transesterification reaction with multifunctional l-aspartic acid monomer to yield OPV-tagged amphiphilic luminescent polyesters. These amphiphilic polyesters self-assembled through strong aromatic π-π stacking and hydrophilic/hydrophobic noncovalent forces into <200 nm size blue-luminescent nanoparticles in aqueous medium. The OPV-tagged polymer nanoparticles served as FRET donor and encapsulated water insoluble Nile Red (NR) fluorophore as a FRET acceptor. Detail photophysical studies revealed that both the OPV and NR were confined within Förster distance in the polymer nanocontainer and the nanodomains provided appropriate geometry for efficient excitation energy transfer from OPV to NR. Cytotoxicity studies in breast cancer (MCF 7), cervical cancer (HeLa) and normal (Wild-type MEF) cell lines revealed that both the nascent luminescent OPV nanoparticles and OPV-NR FRET probes were nontoxic to cells up to 100 μg/mL. Confocal microscope images confirmed the efficient transportation of polymer and FRET probes across the cell membranes and their preferable accumulation in the cytoplasm of the cells. Lysosomal tracker assisted live cell imaging provided direct evidence for the localization of the polymer nanoparticles at the lysosomal compartments in the cytoplasm. In vitro enzyme-responsive studies revealed that the aliphatic polyester backbone in the polymer nanoparticles was readily biodegradable by lysosomal enzymes like esterase, chymotrypsin, trypsin, and also redox GSH species in the cytoplasm. Selective photoexcitation in confocal microscope exhibited bright OPV blue-luminescence and strong red-emission from NR followed by the excitation energy transfer and occurrence of FRET process at the intracellular environment in cancer cell lines. Both the polymer design and the biodegradable polymer FRET concept are completely new; thus, the present approach opens up new platform of research opportunities for natural l-amino acid based luminescent polymer probes for color-tunable bioimaging in cancer cells.

Designing and Modeling of Logic Circuits Based on Switching of the Gated Oligo-Phenylenevinylene Molecule

Molecular electronics seeks to decrease the cost, power consumption and size of devices, using a variety of approaches. However, few attempts have been made to address circuit simulation. The availability of common semiconductor components means they can be used for modeling and simulating molecular circuits to speed progress in molecular electronics. The present study examines the switching of a gated oligo-phenylenevinylene (OPV) molecule as a NMOS molecular transistor, resistance as an indicator of methyl molecules, and the linking of these abilities using LTspice simulation software. The circuit simulation of molecules of basic logic gates, half-adder, full-adder, and multiplier logic circuits are carried out. The numerical results may shed light on the next applications of molecular systems and make them a good, promising candidate for field-effect transistors.

Design and modeling of molecular logic circuits based on transistor structures

Molecular electronics technology removes limitations on miniaturization of semiconductor-based devices. With shrinking device sizes, we can expect smaller but more efficient devices. This branch of research also speeds up the devices, which enables us to have faster processors in the future. In order to have progress in this branch of research, we need to have modeling based on realities. Due to the availability of semiconductor-based devices, they can be used to further the goals of modeling in this field. Here, a specific procedure for the design and modeling of the molecular logic circuit based on the transistor structures is provided. That is, we use the circuit modelling for a gated oligo-phenylene vinylene (OPV) molecule as a NMOS molecular transistor's swithch and a methyl molecule as a resistor. We also benefited from the capabilities of the LTspice simulator software. Connecting these components, we could successfully conduct the circuit simulation of the combinational logic circuits, such as decoder, encoder, multiplexer, and comparator logical molecules, and prove the validity of the model.

Covalently Functionalized SWCNTs as Tailored p-Type Dopants for Perovskite Solar Cells.

The covalent functionalization of (7,6)-enriched single-walled carbon nanotubes (SWCNTs) with oligophenylenevinylene (OPV) moieties terminating with a dimethylamino group is proposed as an efficient way to enhance the affinity of CNTs with spiro-MeOTAD in perovskite-based solar cells. The evidence of SWCNTs functionalization and the degree of OPV substitution on SWCNTs are established from TGA, XPS, TEM, and Raman techniques. Our tailored doping materials afford photovoltaic performances in line with conventional Li-doped spiro-MeOTAD, showing at the same time a significantly improved chemical stability of the perovskite component over time. Furthermore, the comparison of the photovoltaic performances with those obtained with nonfunctionalized SWCNTs suggest that the presence of the organic appends ensures highly reproducible PV performances. These results demonstrate the suitability of this functionalized SWCNT material as a valid doping agent for spiro-MeOTAD, representing a viable alternative to the conventional Li salt.