Synthesis, Electronic Structure, Molecular Packing/Morphology Evolution, and Carrier Mobilities of Pure Oligo-/Poly(alkylthiophenes)

Zhang, Lei; Colella, Nicholas S.; Liu, Feng; Trahan, Stephan; Baral, Jayanta K.; Winter, H. Henning; Mannsfeld, Stefan C. B.; Briseño, Alejandro L.

doi:10.1021/ja3104796

Cited by 99 publications

(139 citation statements)

References 56 publications

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“…GIWAXS can provide details about the crystalline packing of weakly scattering organic materials in thin films, whereas well-ordered films typically exhibit diffraction patterns with a high number of intensive elliptical reflections. 37 In contrast to ordinary XRD measurements, GIWAXS probes the molecular packing in both in-plane ( q xy ) and out-of-plane ( q z ) directions with respect to the film surface. Conventionally, reflections along the out-of-plane and in-plane direction appearing along the q z axis and q xy axis, respectively, are indexed as (00 l ), and ( h 00) and (0 k 0), respectively.…”

Section: Resultsmentioning

confidence: 99%

Free-Standing Monolayer Two-Dimensional Supramolecular Organic Framework with Good Internal Order

et al. 2015

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Utilizing dynamic self-assembly and self-sorting to obtain large-area, molecularly precise monolayered structures represents a promising approach toward two-dimensional supramolecular organic frameworks (2D SOF) or 2D supramolecular polymers. So far, related approaches suffer from small domain sizes, fragility and weak long-range internal order. Here we report on the self-assembly of a host–guest enhanced donor–acceptor interaction, consisting of a tris(methoxynaphthyl)-substituted truxene spacer, and a naphthalene diimide substituted with N-methyl viologenyl moieties as donor and acceptor monomers, respectively, in combination with cucurbit[8]uril as host monomer toward monolayers of an unprecedented 2D SOF. Featuring orthogonal solubility, the participating molecules self-assemble at a liquid–liquid interface, yielding exceptionally large-area, insoluble films, which were analyzed by transmission electron microscopy, atomic force microscopy and optical microscopy to be monolayers with a thickness of 1.8 nm, homogeneously covering areas up to 0.25 cm2, and featuring the ability to be free-standing over holes of 10 μm2. Characterization with ultraviolet–visible absorption spectroscopy, solid-state nuclear magnetic resonance spectroscopy, infrared spectroscopy, and grazing incidence wide-angle X-ray scattering allowed for confirmation of a successful complexation of all three monomers toward an internal long-range order and gave indications to an expected hexagonal superstructure. Our results extend the existing variety of two-dimensional soft nanomaterials by a versatile supramolecular approach, whereas the possibility of varying the functional monomers is supposed to open adaptability to different applications like membranes, sensors, molecular sieves, and optoelectronics.

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Section: Resultsmentioning

confidence: 99%

Free-Standing Monolayer Two-Dimensional Supramolecular Organic Framework with Good Internal Order

et al. 2015

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“…21,22 As a reference compound, PQT12 was first synthesized from oxidative polymerization of QT using ferric chloride as the oxidizing agent. 21,23 In agreement with those previous reports, this procedure led to PQT12 ref with a M n of 22 kDa and a molar-mass dispersity (Đ M ) of 2.2.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

En Route to Defect-Free Polythiophene Derivatives by Direct Heteroarylation Polymerization

2015

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We report the synthesis of well-defined poly(3,3‴-didodecyl-2,2′:5′,2″:5″,2‴-quaterthiophene) (PQT12) from a direct heteroarylation polymerization (DHAP) of 5-bromo-3,3‴-didodecyl-2,2′:5′,2″:5″,2‴-quaterthiophene (monomer A) and 5-bromo-3′,4″-didodecyl-2,2′:5′,2″:5″,2‴-quaterthiophene (monomer B). Experiments with different catalysts, ligands, additives, and solvents have revealed that the utilization of Herrmann−Beller catalyst and P(oNMe 2 Ph) 3 can lead to selective thiophene−thiophene couplings. In this regard, solid-state optical and thermal measurements were particularly useful to detect the presence of β-branching and indicate that minor molecular defects can induce important changes within the supramolecular organization. We also highlight the fact that steric protection around unsubstituted β-positions of α-bromothiophene units is needed to obtain a good selectivity of the crosscouplings at the α-positions. This can be achieved by the presence of a substituent at an adjacent β-position or the utilization of a bulky acidic additive (i.e., neodecanoic acid) in the catalytic system. These synthetic procedures applied to both monomers have led to PQT12 samples showing essentially the same optical and thermal properties and are comparable to those observed with their analogues prepared from chemical oxidation or Stille coupling.

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“…[30] Similar efforts have been devoted to improving n-channel polymer semiconductors, with the performances of n-type devices still lagging behind their p-channel counterparts. [31][32][33][34][35][36] The main obstacle that has traditionally prevented the improvement of electron transporting polymers is the presence of trap sites forming at around −3.8 to −4.0 eV, mainly associated with hydrogenated oxygen, which complicates the design of conjugated polymers because of the requirement for a lowest unoccupied molecular orbital (LUMO) energy level that lays below this range. [37] In the recent past, different solutions have been proposed, among which a remarkably well performing solution-processable n-type polymer reported by Yan et al, based on a naphthalene diimide (NDI) acceptor moiety (referred to as PNDI2OD-T2) and easily achieving fieldeffect mobilities in the 0.1 to 1 cm 2 V −1 s −1 range, represented a breakthrough in the development of n-channel organic polymeric semiconductors.…”

Section: Introductionmentioning

confidence: 99%

High‐Mobility Naphthalene Diimide and Selenophene‐Vinylene‐Selenophene‐Based Conjugated Polymer: n‐Channel Organic Field‐Effect Transistors and Structure–Property Relationship

Sung

Luzio

Park

et al. 2016

Adv Funct Materials

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Interdependence of chemical structure, thin-film morphology, and transport properties is a key, yet often elusive aspect characterizing the design and development of high-mobility, solution-processed polymers for large-area and flexible electronics applications. There is a specific need to achieve >1 cm 2 V −1 s −1 field-effect mobilities (μ) at low processing temperatures in combination with environmental stability, especially in the case of electron-transporting polymers, which are still lagging behind hole transporting materials. Here, the synthesis of a naphthalene-diimide based donor-acceptor copolymer characterized by a selenophene vinylene selenophene donor moiety is reported. Optimized field-effect transistors show maximum μ of 2.4 cm 2 V −1 s −1 and promising ambient stability. A very marked film structural evolution is revealed with increasing annealing temperature, with evidence of a remarkable 3D crystallinity above 180 °C. Conversely, transport properties are found to be substantially optimized at 150 °C, with limited gain at higher temperature. This discrepancy is rationalized by the presence of a surface-segregated prevalently edge-on packed polymer phase, dominating the device accumulated channel. This study therefore serves the purpose of presenting a promising, high-electron-mobility copolymer that is processable at relatively low temperatures, and of clearly highlighting the necessity of specifically investigating channel morphology in assessing the structure-property nexus in semiconducting polymer thin films.

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Synthesis, Electronic Structure, Molecular Packing/Morphology Evolution, and Carrier Mobilities of Pure Oligo-/Poly(alkylthiophenes)

Cited by 99 publications

References 56 publications

Free-Standing Monolayer Two-Dimensional Supramolecular Organic Framework with Good Internal Order

Free-Standing Monolayer Two-Dimensional Supramolecular Organic Framework with Good Internal Order

En Route to Defect-Free Polythiophene Derivatives by Direct Heteroarylation Polymerization

High‐Mobility Naphthalene Diimide and Selenophene‐Vinylene‐Selenophene‐Based Conjugated Polymer: n‐Channel Organic Field‐Effect Transistors and Structure–Property Relationship

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