Imaging the Predicted Isomerism of Oligo(aniline)s: A Scanning Tunneling Microscopy Study

Thomas, James Oscar; Andrade, Hugo Dominguez; Mills, Benjamin M.; Fox, Neil A.; Hoerber, Heinrich; Faul, Charl F. J.

doi:10.1002/smll.201500511

Cited by 11 publications

(14 citation statements)

References 25 publications

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“…We based our initial structures on the isomers and conformations of other oligo(aniline)s determined by X‐ray diffraction,29 NMR spectroscopy,30 and STM,31 then minimised the geometries in Gaussian32 with a widely used DFT method: the B3LYP functional,33 the 6‐31G* basis set,34 and a polarisable continuum model35 (PCM) to account for solvation. The output of this first modelling step can be examined in a variety of ways,36 some of which are illustrated in Figure 2 for the radical cation of TDPB .…”

Section: Resultsmentioning

confidence: 99%

Exploring Redox States, Doping and Ordering of Electroactive Star‐Shaped Oligo(aniline)s

Mills

Fey

Marszałek

et al. 2016

Chemistry A European J

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We have prepared a simple star‐shaped oligo(aniline) (TDPB) and characterised it in detail by MALDI‐TOF MS, UV/Vis/NIR spectroscopy, time‐dependent DFT, cyclic voltammetry and EPR spectroscopy. TDPB is part of an underdeveloped class of π‐conjugated molecules with great potential for organic electronics, display and sensor applications. It is redox active and reacts with acids to form radical cations. Acid‐doped TDPB shows behaviour similar to discotic liquid crystals, with X‐ray scattering investigations revealing columnar self‐assembled arrays. The combination of unpaired electrons and supramolecular stacking suggests that star‐shaped oligo(aniline)s like TDPB have the potential to form conducting nanowires and organic magnetic materials.

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Section: Resultsmentioning

confidence: 99%

Exploring Redox States, Doping and Ordering of Electroactive Star‐Shaped Oligo(aniline)s

Mills

Fey

Marszałek

et al. 2016

Chemistry A European J

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“…Fault et al. demonstrated by low temperature UHV‐STM investigations the importance of isomerism in the self‐assembly of monolayers of emeraldine state Ph/Ph and Ph/C 12 TANI [59] . Those results were fully supported by DFT calculations, and showed that the tetra(aniline) derivatives on a Cu (110) surface form disordered structures.…”

Section: Resultsmentioning

confidence: 92%

Nonlinear Optical and Spectroscopical Properties of Functionalized Oligoanilines

et al. 2021

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Functionalized octamers of polyaniline neutral forms (leucoemeraldine, emeraldine, pernigraniline) were studied in order to optimize the first hyperpolarizabilities (β). Remarkable static β values were found for the pernigraniline and emeraldine derivatives by using the coupled perturbed Kohn-Sham (CPKS) approach at the PBE1PBE/6-31G** level. The enhanced nonlinear response was achieved through the introduction of donor (D) and/or acceptor (A) groups into the oligoanilines structures. The nonlinear optical (NLO) properties of the octamers missing the substituent groups were also investigated. The largest β values were obtained for the pernigraniline and emeraldine derivatives having the tert-butyl (D) and dicyanoethenyl (A) substituents at opposite ends, as well as the ones with only the acceptor group. These oligomers show charge transfer transitions with large oscillator strengths according to the time dependent density functional theory (TD-DFT). Predicted β values for the majority of functionalized oligoanilines strongly indicate them as potential building blocks for molecular-based nonlinear materials with secondorder response.

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“…Unlike EB-state TANI -based materials, [ 24 ] fi lms prepared from ESstate TANI-C 8 (see the Experimental Section for details)…”

Section: Conductive-afm Patterning Of Organic Semiconductorsmentioning

confidence: 99%

“…Unlike EB-state TANI -based materials, [ 24 ] fi lms prepared from ESstate TANI-C 8 (see the Experimental Section for details) The atomic force microscope (AFM) has developed into a mature and widespread topography characterisation tool since its inception in the 1980s. The high resolution and precision nature of this tool has also led to widespread use, under ambient conditions, for diverse applications.…”

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Conductive‐AFM Patterning of Organic Semiconductors

Brown

Picco

Miles

et al. 2015

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local-oxidation nanolithography techniques. [ 17,18 ] This constructive c-AFM redox-writing (cAROW) methodology shows potential for further exploration and development into a scalable, fast write-read technology. [ 19,20 ] The organic semiconductor used in this investigation is based on phenyl/amine-capped tetra(aniline), Ph/NH 2 -TANI , a short-chain, functional, and well-defi ned low molecular weight oligomeric analogue of the well-known conducting polymer, poly(aniline), PANI. Ph/NH 2 -TANI retains the desirable optoelectronic properties of PANI while circumventing the issues of poor solubility, processability, and polydispersity that have previously limited the applications of the polymer. [ 21 ] It is possible to fi ne-tune the optoelectronic properties of tetra(aniline) derivatives, and higher oligomers, simply through modifi cation of the central unit and variation of the end-group functionalization. [ 22 ] Similar to PANI, these oligomeric materials can be reversibly switched (doped) from their conductive emeraldine salt (ES) state to either the nonconductive fully reduced leucoemeraldine base (LEB) or emeraldine base (EB) states through redox, and acid-base chemistry, respectively. [ 23 ] An extensive range of possible inorganic and organic acid dopants exists, with the latter able to simultaneously act as dopants and plasticisers.In this work, N -(4-(((1E,4E)-4-((4-(phenylamino)-phenyl) imino)-cyclohexa-2,5-dien-1-ylidene)amino)phenyl)octanamide ( TANI-C 8 ) doped to the conductive ES state with the prototypical PANI dopant camphorsulfonic acid ( CSA ) was chosen, as this combination formed smooth, continuous thin fi lms on highly oriented pyrolytic graphite (HOPG). Unlike EB-state TANI -based materials, [ 24 ] fi lms prepared from ESstate TANI-C 8 (see the Experimental Section for details) The atomic force microscope (AFM) has developed into a mature and widespread topography characterisation tool since its inception in the 1980s. The high resolution and precision nature of this tool has also led to widespread use, under ambient conditions, for diverse applications. These applications include the direct observation of single-molecule events, [ 1,2 ] molecular force measurements, [ 3,4 ] the fabrication of nanostructures via a variety of nanoscale lithographies, [ 5,6 ] including electrochemical deprotection to yield responsive monolayers, [ 7,8 ] enzymatic oxidative poly merization to locally form conducting polymers, [ 9 ] formation of polymerized sulphur nanostructures, [ 10 ] and direct writing of metallic nanostructures. [ 11 ] These applications were recently classifi ed into mechanical, thermal, diffusive, and electrical processes according to the dominant tip-surface interaction involved. [ 12 ] The last includes probe-based oxidation and reduction lithographies. Although oxidative processes are known, and have been exploited extensively, [13][14][15] reductive processes under ambient conditions are less common.Here we show, in a facile single-step approach, reversible local reductive and oxida...

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Imaging the Predicted Isomerism of Oligo(aniline)s: A Scanning Tunneling Microscopy Study

Cited by 11 publications

References 25 publications

Exploring Redox States, Doping and Ordering of Electroactive Star‐Shaped Oligo(aniline)s

Exploring Redox States, Doping and Ordering of Electroactive Star‐Shaped Oligo(aniline)s

Nonlinear Optical and Spectroscopical Properties of Functionalized Oligoanilines

Conductive‐AFM Patterning of Organic Semiconductors

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