Synthesis, electrochemistry, STM investigation of oligothiophene self-assemblies with superior structural order and electronic properties

Kuo, Cheng -Yu; Liu, Yinghao; Yarotski, Dmitry; Li, Hao; Xu, Ping; Yen, Hung-Ju; Tretiak, Sergei; Wang, Hsing -Lin

doi:10.1016/j.chemphys.2016.05.015

Title: Synthesis, electrochemistry, STM investigation of oligothiophene self-assemblies with superior structural order and electronic properties

Journal Article · Sun Jun 05 00:00:00 EDT 2016 · Chemical Physics

DOI:https://doi.org/10.1016/j.chemphys.2016.05.015· OSTI ID:1477679

Kuo, Cheng -Yu ^[1]; Liu, Yinghao ^[1]; Yarotski, Dmitry ^[1]; Li, Hao ^[1]; Xu, Ping ^[1]; Yen, Hung-Ju ^[1]; Tretiak, Sergei ^[1]; Wang, Hsing -Lin ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Here, three oligothiophene (terthiophene, tetrathiophene and pentathiophene) derivatives are synthesized and their monolayer self-assemblies on gold (Au) are prepared via Au–S covalent bond. Our UV–Vis experimental characterization of solution reveals the dependence of the optical properties on the conjugation length of the oligothiophenes, which compares well with Time-Dependent Density Functional Theory (TDDFT) simulations of spectra of individual chromophores. Photoluminescent spectra of thin films show pronounced red shifts compared to that of solutions, suggesting strong inter-oligomer interactions. The comparative studies of cyclic voltammograms of tetrathiophene from solution, cast film and self-assembled monolayer (SAM) indicate presence of one, two, and three oxidized species in these samples, respectively, suggesting a very strong electronic coupling between tetrathiophene molecules in the SAM. Scanning tunneling microscopy (STM) imaging of SAMs of the tetrathiophene on an atomically flat Au surface exhibits formation of monolayer assemblies with molecular order, and the molecular packing appears to show an overlay of oligothiophene molecules on top of another one. In contrast, the trimer and pentamer images show only aggregated species lacking long-range order on the molecular level. Such trends in going from disordered–ordered–disordered monolayer assemblies are mainly due to a delicate balance between inter-chromophore π–π couplings, hydrophobic interaction and the propensity to form Au–S covalent bond. Such hypothesis has been validated by our computational results suggesting different interaction patterns of oligothiophenes with odd numbered and even numbered thiophene repeat units placed in a dimer configuration. Finally, observed correlations between oligomer geometry and structural order of monolayer assembly elucidate important structure–property relationships and have implications for these molecular structures in organic optoelectronic devices and energy devices.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA); LANL Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1477679

Alternate ID(s):: OSTI ID: 1572427

Report Number(s):: LA-UR-17-27858

Journal Information:: Chemical Physics, Vol. 481; ISSN 0301-0104

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
oligothiophene
self-assembly
spectroscopy
structural order
TDDFT

Title: Synthesis, electrochemistry, STM investigation of oligothiophene self-assemblies with superior structural order and electronic properties

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