Supramolecular organization in fluorene/indenofluorene-oligothiophene alternating conjugated copolymers

A series of conjugated copolymers containing fluorene or indenofluorene units alternating with oligothiophene segments, with potential interest for use as the active layer in field-effect transistors, is investigated. Atomic force microscopy analysis of the morphology of thin deposits shows either the formation of fibrillar structures, which are the signature of long-range π stacking, or the presence of untextured aggregates, resulting from disordered assembly. These morphologies are interpreted in terms of the supramolecular organization of the conjugated chains. Molecular modeling simulations indicate that the commensurability between the lengths of the monomer units and the presence of alkyl side groups are the two key structural factors governing the chain organization into highly ordered assemblies. The most favorable structures are those combining fluorene (indenofluorene) units with unsubstituted bithiophene (terthiophene) segments.

Supramolecular ordering in oligothiophene−fullerene monolayers

Scanning tunneling microscopy (STM) of monolayers comprising oligothiophene and fullerene molecular semiconductors reveals details of their molecular-scale phase separation and ordering with potential implications for the design of organic electronic devices, in particular future bulk heterojunction solar cells. Prochiral terthienobenzenetricarboxylic acid (TTBTA) self-assembles at the solution/graphite interface into either a porous chicken wire network linked by dimeric hydrogen bonding associations of COOH groups (R22(8)) or a close-packed network linked in a novel hexameric hydrogen bonding motif (R66(24)). Analysis of high-resolution STM images shows that the chicken wire phase is racemically mixed, whereas the close-packed phase is enantiomerically pure. The cavities of the chicken wire structure can efficiently host C60 molecules, which form ordered domains with either one, two, or three fullerenes per cavity. The observed monodisperse filling and long-range co-alignment of fullerenes is described in terms of a combination of an electrostatic effect and the commensurability between the graphite and molecular network, which leads to differentiation of otherwise identical adsorption sites in the pores.

Molecular structure of the discotic liquid crystalline phase of hexa-peri-hexabenzocoronene/oligothiophene hybrid and their charge transport properties

Using atomistic molecular dynamics simulation, we study the discotic columnar liquid crystalline (LC) phases formed by a new organic compound having hexa-peri-Hexabenzocoronene (HBC) core with six pendant oligothiophene units recently synthesized by Nan Hu et al. Adv. Mater. 26, 2066 (2014)]. This HBC core based LC phase was shown to have electric field responsive behavior and has important applications in organic electronics. Our simulation results confirm the hexagonal arrangement of columnar LC phase with a lattice spacing consistent with that obtained from small angle X-ray diffraction data. We have also calculated various positional and orientational correlation functions to characterize the ordering of the molecules in the columnar arrangement. The molecules in a column are arranged with an average twist of 25 degrees having an average inter-molecular separation of similar to 5 angstrom. Interestingly, we find an overall tilt angle of 43 degrees between the columnar axis and HBC core. We also simulate the charge transport through this columnar phase and report the numerical value of charge carrier mobility for this liquid crystal phase. The charge carrier mobility is strongly influenced by the twist angle and average spacing of the molecules in the column. (C) 2015 AIP Publishing LLC.

Optimization of solution-processed oligothiophene:fullerene based organic solar cells by using solvent additives

The optimization of solution-processed organic bulk-heterojunction solar cells with the acceptor-substituted quinquethiophene DCV5T-Bu-4 as donor in conjunction with PC61BM as acceptor is described. Power conversion efficiencies up to 3.0% and external quantum efficiencies up to 40% were obtained through the use of 1-chloronaphthalene as solvent additive in the fabrication of the photovoltaic devices. Furthermore, atomic force microscopy investigations of the photoactive layer gave insight into the distribution of donor and acceptor within the blend. The unique combination of solubility and thermal stability of DCV5T-Bu-4 also allows for fabrication of organic solar cells by vacuum deposition. Thus, we were able to perform a rare comparison of the device characteristics of the solution-processed DCV5T-Bu-4:PC61BM solar cell with its vacuum-processed DCV5T-Bu-4:C-60 counterpart. Interestingly in this case, the efficiencies of the small-molecule organic solar cells prepared by using solution techniques are approaching those fabricated by using vacuum technology. This result is significant as vacuum-processed devices typically display much better performances in photovoltaic cells. Keywords

STM study on the self-assembly of oligothiophene-based organic semiconductors

The self-assembly properties of a series of functionalized regioregular oligo(3-alkylthiophenes) were investigated by using scanning tunneling microscopy (STM) at the liquid-solid interface under ambient conditions. The characteristics of the 2-D crystals formed on the (0001) plane of highly ordered pyrolitic graphite (HOPG) strongly depend on the length of the p-conjugated oligomer backbone, on the functional groups attached to it, and on the alkyl substitution pattern on the individual thiophene units. Theoretical calculations were performed to analyze the geometry and electronic density of the molecular orbitals as well as to analyze the intermolecular interactions, in order to obtain models of the 2-D molecular ordering on the substrate.

Film Morphology and Molecular Orientation in Oligothiophene-fluorene Films

The effects of processing conditions on film morphology and molecular orientation were studied for a novel conjugated fluorene-bithiophene oligomer, oligo(9,9-dioctylfluorene-alt-bithiophene) (OF8T2). Depending on the method of film preparation, OF8T2 molecules adopt different orientations in the films. X-ray diffraction peak at 4.9 degrees of the OF8T2 film deposited from petroleum ether/dichloromethane mixture is attributed to a layering distance between sheets of OF8T2 chains, which are separated by the octyl side chains. Preferred orientation is clearly inferred through the absence of peaks corresponding to pi-pi stacking.

Poly(oligothiophene-alt-benzothiadiazole)s: Tuning the Structures of Oligothlophene Units toward High-Mobility "Black" Conjugated Polymers

A series of donor-acceptor low-bandgap conjugated polymers, i.e., PTnBT (n = 2-6), composed of alternating oligothiophene (OTh) and 2,1,3-benzothiadiazole (BT) units were synthesized by Stille cross-coupling polymerization. The number of thiophene rings in OTh units, that is n, was tuned from 2 to 6. All these polymers display two absorption bands in both solutions and films with absorption maxima depending on n. From solution to film, absorption spectra of the polymers exhibit a noticeable red shift. Both high- and low-energy absorption bands or P'F5BT and PT6BT films locate in the visible region, which are at 468 and 662 nm for PT5BT and 494 and 657 nm for PT6BT.

A rapid solid-phase synthesis to soluble oligothiophene molecular wires

A novel method for the preparation of oligothiophene molecular wires is described via a bi-directional solid-phase synthesis. Using an alternating sequence of bromination and Stille coupling reactions, oligomers were obtained up to the heptamer in excellent yield and purity.

Materials design for ambipolar devices: tuning orbital energetics in oligothiophene-naphthalimides semiconductors

Ambipolar organic field-effect transistors (OFETs), which can efficiently transport both holes and electrons, using a single type of electrode, are currently of great interest due to their possible applications in complementary metal oxide semiconductor (CMOS)-like circuits, sensors, and in light-emitting transistors. Several theoretical and experimental studies have argued that most organic semiconductors should be able to transport both types of carrier, although typically unipolar behavior is observed. One factor that can compromise ambipolar transport in organic semiconductors is poor solid state overlap between the HOMO (p-type) or LUMO (n-type) orbitals of neighboring molecules in the semiconductor thin film. In the search of low-bandgap ambipolar materials, where the absence of skeletal distortions allows closer intermolecular π-π stacking and enhanced intramolecular π-conjugation, a new family of oligothiophene-naphthalimide assemblies have been synthesized and characterized, in which both donor and acceptor moieties are directly conjugated through rigid linkers. In previous works we found that oligothiophene-napthalimide assemblies connected through amidine linkers (NDI derivates) exhibit skeletal distortions (50-60º) arising from steric hindrance between the carbonyl group of the arylene core and the sulphur atom of the neighbored thiophene ring (see Figure 1). In the present work we report novel oligo- and polythiophene–naphthalimide analogues NAI-3T, NAI-5T and poly-NAI-8C-3T, in which the connections of the amidine linkage have been inverted in order to prevent steric interactions. Thus, the nitrogen atoms are directly connected to the naphthalene moiety in NAI derivatives while they were attached directly to the thiophene moiety in the previously investigated NDI-3T and NDI-5T. In Figure 1 is depicted the calculated molecular structure of NAI-3T together with that of NDI-3T showing how the steric interactions are not present in the novel NAI derivative. The planar skeletons in these new family induce higher degree of crystallinity and the carrier charge transport can be switched from n-type to ambipolar behaviour. The highest FET performance is achieved for vapor-deposited films of NAI-3T with mobilities of 1.95x10-4cm2V-1s-1 and 2.00x10-4cm2V-1s-1 for electrons and holes, respectively. Finally, these planar semiconductors are compared with their NDI derivates analogues, which exhibit only n-type mobility, in order to understand the origin of the ambipolarity in this new series of molecular semiconductors.

Synthesis and Self-Assembly of Donor-Acceptor-Donor Based Oligothiophenes and Their Optoelectronic Properties

In this work, the synthesis of an oligothiophene having a donor acceptor donor (D-A-D) chromophore with hydrogen bonding groups is described. The D-A-D molecule was demonstrated to self-organize via intermolecular H-bonding between barbituric acid units. Interactions between the oligothiophene subunits were also found to be important, affording nanoribbons that could be observed by atomic force and transmission electron microscopy. The applicability of the oligothiophene for organic electronic applications was investigated by fabricating organic field-effect transistors (OFETs) and organic photovoltaic devices. The OFET measurements yielded p-type mobility of 7 x 10(-7) cm(2)/(Vs), and when blended with C(60)-PCBM, the photovoltaic efficiency was observed to be 0.18%.

Acenaphtho[1,2-b]quinoxaline based low band gap copolymers for organic thin film transistor applications

We report the synthesis of a novel class of low band gap copolymers based on anacenaphtho[1,2-b]quinoxaline core and oligothiophene derivatives acting as the acceptor and the donor moieties, respectively. The optical properties of the copolymers were characterized by ultraviolet-visible spectroscopy while the electrochemical properties were determined by cyclic voltammetry. The band gap of these polymers was found to be in the range 1.8-2.0 eV as calculated from the optical absorption band edge. X-ray diffraction measurements show weak pi-pi stacking interactions between the polymer chains. The hole mobility of the copolymers was evaluated using field-effect transistor measurements yielding values in the range 10(-5)-10(-3) cm(2)/Vs.

Cyclopentac]thiophene oligomers based solution processable D-A copolymers and their application as FET materials

Two new solution processable, low band gap donor-acceptor (D-A) copolymers (P1 and P2) comprising a cyclopentac] thiophene (CPT) based oligomers as donors and benzoc]1,2,5] selenadiazole (BDS) and 2-dodecyl1,2,3]-benzotriazole (BTAz) as acceptors were synthesized and characterized and their field effect transistor properties were studied. The internal charge transfer interaction between the electron-donating CPT based oligothiophene and the electron-accepting BDS or BTAz unit effectively reduces the band gap in polymers to 1.3 and 1.66 eV with low lying highest occupied molecular orbital (HOMO). The absorption spectrum of P1 was found to be more red shifted than that of P2 because of incorporation of the more electron-withdrawing BDS unit. The color of neutral P1 was found to be green in both solution and film states with two major bands in the absorption spectra; however, neutral P2 revealed one dominant absorption exhibiting red color in both solution and film state which could be attributed to the less electron-withdrawing effect of the BTAz unit. The polymers were further characterized by GPC, TGA, DSC and cyclic voltammetry. P1 and P2 exhibited charge carrier mobilities as high as 9 x 10(-3) cm(2) V-1 s(-1) and 2.56 x 10(-3) cm 2 V-1 s(-1), respectively with the current on/off ratio (I-on/I-off) in the order of 10(2).

Novos compostos orgânicos reticuláveis para aplicações em células fotovoltaicas

Trabalho Final de Mestrado para obtenção do grau de mestre em Engenharia Química e Biológica

Synthesis, multiscale-multiphase characterization and applications of thiophene-based biohybrids

Biohybrid derivatives of π-conjugated materials are emerging as powerful tools to study biological events through the (opto)electronic variations of the π-conjugated moieties, as well as to direct and govern the self-assembly properties of the organic materials through the organization principles of the bio component. So far, very few examples of thiophene-based biohybrids have been reported. The aim of this Ph. D thesis has been the development of oligothiophene-oligonucleotide hybrid derivatives as tools, on one side, to detect DNA hybridisation events and, on the other, as model compounds to investigate thiophene-nucleobase interactions in the solid state. To obtain oligothiophene bioconjugates with the required high level of purity, we first developed new synthetic ecofriendly protocols for the synthesis of thiophene oligomers. Our innovative heterogeneous Suzuki coupling methodology, carried out in EtOH/water or isopropanol under microwave irradiation, allowed us to obtain alkyl substituted oligothiophenes and thiophene based co-oligomers in high yields and very short reaction times, free from residual metals and with improved film forming properties. These methodologies were subsequently applied in the synthesis of oligothiophene-oligonucleotide conjugates. Oligothiophene-5-labeled deoxyuridines were synthesized and incorporated into 19-meric oligonucletide sequences. We showed that the oligothiophene-labeled oligonucletide sequences obtained can be used as probes to detect a single nucleotide polymorphism (SNP) in complementary DNA target sequences. In fact, all the probes showed marked variations in emission intensity upon hybridization with a complementary target sequence. The observed variations in emitted light were comparable or even superior to those reported in similar studies, showing that the biohybrids can potentially be useful to develop biosensors for the detection of DNA mismatches. Finally, water-soluble, photoluminescent and electroactive dinucleotide-hybrid derivatives of quaterthiophene and quinquethiophene were synthesized. By means of a combination of spectroscopy and microscopy techniques, electrical characterizations, microfluidic measurements and theoretical calculations, we were able to demonstrate that the self-assembly modalities of the biohybrids in thin films are driven by the interplay of intra and intermolecular interactions in which the π-stacking between the oligothiophene and nucleotide bases plays a major role.