Oligoaryl Cruciform Structures as Model Compounds for Coordination‐Induced Single‐Molecule Switches

Grunder, Sergio; Huber, R.; Wu, Songmei; Schönenberger, Christian; Calame, Michel; Mayor, Marcel

doi:10.1002/ejoc.200901150

Cited by 25 publications

(24 citation statements)

References 82 publications

(113 reference statements)

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“…An in situ deprotection and reprotection procedure was chosen to avoid disulfide formation. [220] [221] Since an acetyl protection group is not stable under basic condition it was not suitable for the following Suzuki reaction and another transprotection step was done. The acetyl protecting group of 40 was deprotected to the free thiole 41 by hydrochloric acid which was generated in situ with methanol and acetyl chloride in dichloromethane.…”

Section: Synthesis and Characterization Of Sulfur Functionalized Azo mentioning

confidence: 99%

Shape‐Switchable Azo‐Macrocycles

et al. 2009

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The synthesis of four shape‐switchable macrocycles comprising different peripheral substituents is described. The macrocycles 1–4 consist of m‐terphenyl semicircles interlinked by two azo joints. These macrocycles were assembled from nitro‐functionalized m‐terphenyl moieties through reductive dimerization. The semicircles were assembled through Suzuki cross‐coupling reactions. The molecular weights of the macrocycles were determined by vapour pressure osmometry, because mass spectrometry failed in the cases of 2 and 3. The E → Z photoisomerization reactions were analysed by UV/Vis spectroscopy complemented by 1H NMR studies. A very slow thermal back‐reaction indicated considerable stabilization of the Z isomer. The reduced efficiency of the thermal back‐reaction probably arises from the reduced degree of freedom due to the mechanical interlinking of the two azo groups. The photostationary state consisted of all‐Z (85 %) and all‐E isomers (15 %). The E → Z transformation induced by irradiation displayed simple exponential kinetics, which indicates pairwise switching of the two azo groups in a macrocycle, at least on the timescale under investigation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Synthesis and Characterization Of Sulfur Functionalized Azo mentioning

confidence: 99%

Shape‐Switchable Azo‐Macrocycles

et al. 2009

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“…However, transport studies based on model compounds synthesized within this project revealed the electronically superior coupling via a terminal thiophenol compared to a terminal pyridine subunit, in spite of the shorter electrode-electrode distance in the later case. [10] The first generation of cruciforms consisted of a sulfur-functionalized oligophenylenevinylene (OPV) fixation bar and a transversal pyridine-functionalized oligophenyleneethynylene (OPE) bar (Fig. 2).…”

Section: Molecular Designmentioning

confidence: 99%

“…We proposed a new switching concept based on the interplay between the integrated molecule and the electrodes, designed and synthesized the required molecules and investigated their transport properties. [9,10] The hypothesized switching concept relies on a structure consisting of two rigid-rod type π-systems which cross each other resulting in a molecular cruciform. Both π-systems as bars of the cruciform differ in their electronic transparency and in their terminal anchor groups to the electrodes.…”

Section: Introductionmentioning

confidence: 99%

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Novel Cruciform Structures as Model Compounds for Coordination Induced Single Molecule Switches

Grunder

Huber

et al. 2010

Chimia

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We have synthesized various molecular cruciforms consisting of two different crossing π-systems and comprising crosswise arranged thiol- and pyridine-anchor groups. With these model compounds we strive towards the investigation of a new switching concept based on the potential dependent coordination of pyridines to gold electrodes in an electrochemical set-up. Integration of these cruciform molecules between both electrodes of a mechanically controlled break junction in a liquid environment gave insight into their single molecule transport properties. These studies allowed individual transport characteristics to be assigned to the bar subunits of the cruciforms but also revealed the remaining experimental challenges to realize the suggested switching concept.

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“…We have been exploiting this technique extensively over the past years to determine some of the basic mechanisms at stake in the formation of molecular junctions. [21][22][23][24][25][26][27][28][29] Some examples are provided in the next section.…”

Section: Contacting Strategiesmentioning

confidence: 99%

Molecular Junctions: From Tunneling to Function

Calame

2010

Chimia

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Abstract:Thankstothedevelopmentofappropriateexperimentaltechniques,moleculardevicesandtheirelectricaltransportpropertieshaverecentlybeenthefocusofamajorresearcheffort.Thisbriefreviewdescribeshow individualmoleculescanbecontactedwithmetallicelectrodestoformmolecularjunctionsandaddressestheir basicformationmechanisms.Anextensiontomolecularjunctionsnetworksisalsodiscussed.Functionalitycould bedemonstratedinsuchsystems,andexampleswhereconductancemodulationusinglightorchemicalstimuli wasachievedwillbepresented.

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Oligoaryl Cruciform Structures as Model Compounds for Coordination‐Induced Single‐Molecule Switches

Cited by 25 publications

References 82 publications

Shape‐Switchable Azo‐Macrocycles

Shape‐Switchable Azo‐Macrocycles

Novel Cruciform Structures as Model Compounds for Coordination Induced Single Molecule Switches

Molecular Junctions: From Tunneling to Function

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