Single Electron Tunneling through a Tailored Arylthio-coronene

Kowalzik, P.; Atodiresei, Nicolae; Gingras, Marc; Caciuc, Vasile; Blügel, Stefan; Waser, Rainer; Karthäuser, Silvia

doi:10.1021/jp2018007

Cited by 9 publications

(13 citation statements)

References 32 publications

(44 reference statements)

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“…However, DPTC is a complex large molecule with many rotational degrees of freedom leading to many possible structural conformers. 34 Regarding an ''up-down'' conformer coming from a release of steric hindrance, 9 it is obvious that strong interactions of the core with the HOPG(0001) surface are excluded because the core is screened by the phenyl groups and cannot bind to the surface. Only weaker interactions with phenyl or thioether groups are possible.…”

Section: Supramolecular Self-assemblymentioning

confidence: 99%

“…In spite of a tremendous number of persulfurated aromatic derivatives in the literature, surface studies by STM/STS were performed only recently by some of us, 9 even if the first member of this family of compounds was reported in 1957. 10 Aromatic thioether (sulfide) groups are largely unexplored as an anchoring unit to substrates.…”

Section: Introductionmentioning

confidence: 99%

“…In this study, we focus on the most simple molecular asterisk with a coronene core incorporating twelve non-functionalized arylthio groups, namely dodecakis(phenylthio)coronene (DPTC), and its propensity to make new supramolecular columnar selfassemblies on gold surfaces. In spite of a tremendous number of persulfurated aromatic derivatives in the literature, surface studies by STM/STS were performed only recently by some of us, 9 even if the first member of this family of compounds was reported in 1957. 10 Aromatic thioether (sulfide) groups are largely unexplored as an anchoring unit to substrates.…”

Section: Introductionmentioning

confidence: 99%

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Columnar self-assembly of a 3D-persulfurated coronene asterisk. The dominant role of aryl-sulfur bonds

et al. 2012

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The synthesis, adsorption behavior, surface structure, and the charge transport properties of a persulfurated coronene asterisk with a 3D-polyaromatic system, namely dodecakis(phenylthio)coronene (DPTC), deposited on HOPG(0001) and Au(111) surfaces, are investigated by means of scanning tunneling microscopy (STM) and spectroscopy (STS). DPTC molecules adsorbed on HOPG (0001) show an orbital mediated tunneling through mainly undisturbed frontier molecular states. DPTC molecules self-assemble on Au(111) into a highly ordered p-stacked columnar ''edge-on pattern. The columnar stacking is a gold surface mediated process, as ascertained by fluorescence correlation spectroscopy (FCS). DPTC was monomeric in the precursor solution before assembly. The tunneling spectra of ordered DPTC stacks on Au (111) show an energetic splitting of the frontier molecular states, indicating orbital overlap and supramolecular p-p interactions of adjacent molecules. DPTCs are sufficiently flexible to facilitate dense 1D stacks. The multiple aryl-sulfur bonds play a dominant role in the modulation of the self-assembly properties of the coronenes which in turn affect their electronic properties. Our results encourage further applications in dendrimer chemistry toward molecular electronics, by using the functionalized coronene core and its multidirectional 3D properties.

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Section: Supramolecular Self-assemblymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Columnar self-assembly of a 3D-persulfurated coronene asterisk. The dominant role of aryl-sulfur bonds

et al. 2012

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“…A double-barrier tunnel junction is formed in this way and leads to the occurrence of single electron tunnelling effects in STS measurements. 22…”

Section: Spectroscopic Characteristics and Electronic Functionmentioning

confidence: 99%

“…(b) show that the molecules seem to lie on the surface in a face-on configuration with the coronene core oriented parallel to the surface. The magnified STM image of Fig.4(b) reveals that DMPTCs form a monolayer structure with hexagonal ordering on a short range and an intermolecular distance of (1.75 AE 0.20) nm 22. …”

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confidence: 98%

Arylthio-substituted coronenes as tailored building blocks for molecular electronics

Kowalzik

Atodiresei

Gingras

et al. 2012

Phys. Chem. Chem. Phys.

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The electron transport through molecules in molecular devices is typically influenced by the nature of the interfaces with the contacting electrodes and by the interactions between neighbouring molecules. It is a major goal of molecular electronics to adjust the electronic function of a molecular device by tailoring the intrinsic molecular properties and the interfacial and intermolecular interactions. Here, we report on the tunability of the electronic properties of coronene derivatives, namely dodecakis(arylthio)coronenes (DATCs), which are found to exhibit a three-dimensional aromatic system. Scanning tunnelling microscopy (STM), spectroscopy (STS) and simulations based on the density functional theory (DFT) are employed to characterize the structural and electronic properties of these molecules deposited on Au(111) surfaces. It is shown that modifications of the peripheral aryl-groups allow us to specifically affect the self-assembly and the charge transport characteristics of the molecules. Molecular assemblies like supramolecular wires with highly delocalized orbitals and single molecules with molecular ''quantum dot'' characteristics are obtained in this way.

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Ferrocenes with a Persulfurated Cyclopentadienyl Ring: Synthesis, Structural Studies, and Optoelectronic Properties

Blockhaus

Klein-Heßling

Zehetmaier

et al. 2019

Chemistry A European J

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Persulfurateda renes are af ascinating class of functional molecules with aw ider ange of potentiala pplications. Ferrocenes are also am ultifaceted class of aromatic compounds that can easily be finetuned for an enormous variety of desired properties. Ac ombinationo f both substancec lasses might yield an even wider field of applications. Herein, we describe the synthesis of two ferrocenesw ith one persulfurated cyclopentadienyl ring [C 5 (SR) 5 ], with R = Me or Ph, together with their crystal structures, optical, and electrochemical properties. Both crystal structures show significant intramolecular sulfuriron interactions as well as weak intermoleculars ulfurcontacts. Cyclovoltammetry of the [C 5 (SPh) 5 ]c ompound shows ah igho xidationp otentialo f6 51 mV vs. FcH/FcH + .Persulfurated arenes still remain an underexploited field of chemistry,d espite their highly interesting physical organic properties and their numerous possible applications, ranging from ion-selectivem embranes over organic conductors and ferromagnets to cation sensors andl iquid crystals. [1] This statement made by M. Gingras in af ascinatingr eview article in this journal more than 10 years ago is still valid. There have been, however,s everali nteresting additions to this field, particularly with extended aromatic systems. Per(arylthio)corannulenes and -coronenes have found potential applicationa sp hotovoltaic devices [2] and for molecular electronics. [3] Substituted hexakis(phenylthio)benzenes showeds trong phosphorescence in the solid state with the potential of OLED applications. [4] Dendrimersw ith a[ C 6 (SAr) 6 ]c ore, so-called" molecular asterisks" have been used as multifunctional ligandsf or the preparation of luminescents ensors and asymmetric metal catalysis. [5] The interesting electronic properties sharedb yt his compound class are mainly due to the fact that "phenylthio substituents attached to aromatic cores result in ar eduction of the HOMO-LUMOg ap", [1, 2a] "primarily due to LUMO stabilization". [6] Upon addition of SPh groups ab athochromic shift of the longest wavelength absorption by 10-15 nm is observed together with an increaseofthereductionpotential by 0.1 V. [2b] Metallocenes are another very important group of aromatics with very interestinge lectronic properties. However,w hile quite af ew metal-freep ersulfurated arenes have been studied, there seem to be no reports of persulfuratedferrocenes. The fivefolds ymmetry of metallocenes would create as tructural motifr arely found with thioether-based "moleculara sterisks" (Scheme 1). [7] While the syntheses of persulfurated cyclopentadienyl anions[ C 5 (SR) 5 ] À (R = Me, Ph) was already reported in the 1980s, [8] attempts to prepare metallocenes from them via reactions with metal halidesm et with failure. However,t he complexes[ C 5 (SMe) 5 ]ML n (ML n = Mn(CO) 3 ,R uCp*) could be obtainedv ia post-functionalization of an already coordinated cyclopentadienyl ring. [9,10] Transfer of this syntheticp rotocol using perhalogenatedo rp ermercurated ferroce...

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Single Electron Tunneling through a Tailored Arylthio-coronene

Cited by 9 publications

References 32 publications

Columnar self-assembly of a 3D-persulfurated coronene asterisk. The dominant role of aryl-sulfur bonds

Columnar self-assembly of a 3D-persulfurated coronene asterisk. The dominant role of aryl-sulfur bonds

Arylthio-substituted coronenes as tailored building blocks for molecular electronics

Ferrocenes with a Persulfurated Cyclopentadienyl Ring: Synthesis, Structural Studies, and Optoelectronic Properties

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