Light-Triggered Conductance Switching in Single-Molecule Dihydroazulene/Vinylheptafulvene Junctions

Lara‐Avila, Samuel; Danilov, Andrey; Kubatkin, Sergey; Broman, Søren Lindbæk; Parker, Christian R.; Nielsen, Mogens Brøndsted

doi:10.1021/jp205638b

Cited by 56 publications

(56 citation statements)

References 30 publications

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“…Thus, the dimethylamino group is rate-enhancing due to its strong electron-donation into the sevenmembered ring, whereas the cyano group is rate-enhancing on the account of its electron-withdrawing effect upon the dicyanoethylene unit making the ring closure (for this VHF), the fastest recorded with a half-life of only 21 min. [10] The DHA absorption maxima is only weakly affected by the presence of a substituent in either positions 2 or 7, whereas the VHF absorption is weakly affected by the presence of a substituent in the five-membered ring, but strongly affected by a substituent in the seven-membered ring (Figure 7). In comparison, the half-life of the "parent" compound (Y, X = H) is 206 min.…”

Section: Resultsmentioning

confidence: 99%

Linear Free‐Energy Correlations for the Vinylheptafulvene Ring Closure: A Probe for Hammett σ Values

Broman

Jevric

Nielsen

2013

Chemistry A European J

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Linear free-energy relationships, like Hammett correlations, are fundamental in physical organic chemistry for the elucidation of reaction mechanisms. In this work, we show that Hammett correlations exist for the ring closure of six different model systems of vinylheptafulvenes (VHFs) to their corresponding dihydroazulenes (DHAs). These first-order reactions were easily followed by UV/Vis absorption spectroscopy on account of the significantly different absorption characteristics between VHFs and DHAs. Opposing effects displayed by substituent groups at two different positions are conveniently accounted for by simply subtracting the two Hammett σ values of each group. The linear correlations readily allow us to obtain unknown and approximate Hammett σ values for previously uninvestigated substituents. We also show that they can provide alternative values to the standard ones. We present values for a variety of substituent groups ranging from alkynes, sulfones, sulfoxides, and different heteroaromatics. The electronic effects exerted by substituent groups on VHFs are also reflected in their absorption maxima. Thus, we have established an empirical relationship between the absorption maximum of the VHF and the Hammett σ values of its substituents. This fine-tuning of electronic properties is particularly important for the ongoing efforts of using the DHA/VHF molecular switch in molecular electronics devices.

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Section: Resultsmentioning

confidence: 99%

Linear Free‐Energy Correlations for the Vinylheptafulvene Ring Closure: A Probe for Hammett σ Values

Broman

Jevric

Nielsen

2013

Chemistry A European J

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“…30). 241,242 The reproducibility and robustness of this molecule in single molecule transport measurements has been demonstrated by more than 20 ''ON-OFF'' cycles. By analysing the experimental conductance data, the authors of this report concluded that electric transport through both DHA (high resistivity) and VHF (low resistivity) isomers occurs by sequential tunnelling.…”

Section: Molecular Switchesmentioning

confidence: 99%

Single-molecule electronics: from chemical design to functional devices

et al. 2014

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The use of single molecules in electronics represents the next limit of miniaturisation of electronic devices, which would enable us to continue the trend of aggressive downscaling of silicon-based electronic devices. More significantly, the fabrication, understanding and control of fully functional circuits at the single-molecule level could also open up the possibility of using molecules as devices with novel, not-foreseen functionalities beyond complementary metal-oxide semiconductor technology (CMOS). This review aims at highlighting the chemical design and synthesis of single molecule devices as well as their electrical and structural characterization, including a historical overview and the developments during the last 5 years. We discuss experimental techniques for fabrication of single-molecule junctions, the potential application of single-molecule junctions as molecular switches, and general physical phenomena in single-molecule electronic devices.

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“…Previous work investigated the conductance switching effects on single molecules through electrochemical gating, [11][12][13][14][15][16][17][18][19] photo switching, [20][21][22][23][24][25][26][27] and mechanically controlling molecular configurations. [28] The few prior reports of the modulation of molecular conductance through changes in the solution pH show either a small switching effect (on/off ratio of about 2), [29] or the detection of only one state at one pH, presumably the high conductance state, while the conductance value of the second state was not detected, either because a junction could not be formed or the conductance was too low.…”

Section: Angewandte Chemiementioning

confidence: 99%

Single‐Molecule Sensing of Environmental pH—an STM Break Junction and NEGF‐DFT Approach

Smeu

Afsari

et al. 2013

Angewandte Chemie

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We thank Vu Nguyen and Navin Rao for help with measuring the UV/Vis spectra of the dye molecules. We thank the National Science Foundation (CHE 0809838 to E.B., CHE-1058896 to M.S., CHE-1058896 to M.A.R.) and the FRQNT (M.S.) for financial support. STM = scanning tunneling microscopy, NEGF-DFT = density functional theory calculations carried out under framework of the nonequilibrium Green's function.Supporting information for this article is available on the WWW under http://dx.

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Light-Triggered Conductance Switching in Single-Molecule Dihydroazulene/Vinylheptafulvene Junctions

Cited by 56 publications

References 30 publications

Linear Free‐Energy Correlations for the Vinylheptafulvene Ring Closure: A Probe for Hammett σ Values

Linear Free‐Energy Correlations for the Vinylheptafulvene Ring Closure: A Probe for Hammett σ Values

Single-molecule electronics: from chemical design to functional devices

Single‐Molecule Sensing of Environmental pH—an STM Break Junction and NEGF‐DFT Approach

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