Facile synthesis of oligoyne amphiphiles and their rotaxanes

Schrettl, Stephen; Contal, Emmanuel; Hoheisel, Tobias N.; Fritzsche, Martin; Balog, Sandor; Szilluweit, Ruth; Frauenrath, Holger

doi:10.1039/c4sc03154g

Cited by 60 publications

(37 citation statements)

References 69 publications

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“…13 A recent approach to oligoyne stabilization has been "insulation" of the oligoyne by threading through the cavity of a macrocycle, to give a rotaxane. [14][15][16][17] Metal centers have also been widely used as stabilizing end-caps to give complexes with the stoichiometry, [{L m M}{μ-(C≡C) n }{ML m }] x+ , which have provided interesting test-beds for examination of their electronic, physical and chemical properties as a function of metal oxidation state. 18 In 4 particular, electronic and vibrational spectroscopies of complexes of this type, coupled with detailed computational investigations, have enabled electronic structures of the all-carbon chain bridged complexes to be assessed.…”

Section: Introductionmentioning

confidence: 99%

Solvent Dependence of the Single Molecule Conductance of Oligoyne-Based Molecular Wires

et al. 2015

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Citation for published item:wil nD h vid gF nd elEyw ediD yd y eF nd yerthelD w rieEghristine nd w rqu¡ esEqonz¡ lezD nti go nd frookeD i h rd tF nd fry eD w rtin F nd ge D il r nd perrerD t ime nd rigginsD imon tF nd v m ertD golin tF nd vowD ul tF nd solt w nriqueD h vid nd w rtinD nti go nd xi holsD i h rd tF nd hw rz herD lther nd q r ¡ % E u¡ rezD ¡ % tor wF @PHITA 9 olvent dependen e of the single mole ule ondu t n e of oligoyneE sed mole ul r wiresF9D tourn l of physi l hemistry gFD IPH @PWAF ppF ISTTTEISTURF Further information on publisher's website:This document is the Accepted Manuscript version of a Published Work that appeared in nal form in The Journal of Physical Chemistry C, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see http://dx.doi.org/10.1021/acs.jpcc.5b08877. Additional information:Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

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Section: Introductionmentioning

confidence: 99%

Solvent Dependence of the Single Molecule Conductance of Oligoyne-Based Molecular Wires

et al. 2015

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“…The successful synthesis is confirmed by the 13 C NMR spectrum (Figure 1b) as well as the UV-Vis absorption spectrum (Figure 1c) 31,54 . This demonstrates the facile nature by which higher oligoyne homologues can be prepared by the developed synthetic methodology 30,31 . However, it is important to keep the sensitivity of oligoyne derivatives in mind, and their storage in dilute solutions is advisable in order to ensure long-term integrity.…”

Section: Discussionmentioning

confidence: 55%

“…The desired hexayne amphiphile (3) is straightforwardly prepared by the sequential bromination 52,53 and Pd-catalyzed elongation 30,31 of the alkyne segment, followed by a final deprotection reaction of the tritylphenyl ester (2) (Figure 1a) 29 . The successful synthesis is confirmed by the 13 C NMR spectrum (Figure 1b) as well as the UV-Vis absorption spectrum (Figure 1c) 31,54 .…”

Section: Discussionmentioning

confidence: 99%

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Preparation of Carbon Nanosheets at Room Temperature

Schrettl

Schulte

Stefaniu

et al. 2016

JoVE

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Amphiphilic molecules equipped with a reactive, carbon-rich "oligoyne" segment consisting of conjugated carbon-carbon triple bonds selfassemble into defined aggregates in aqueous media and at the air-water interface. In the aggregated state, the oligoynes can then be carbonized under mild conditions while preserving the morphology and the embedded chemical functionalization. This novel approach provides direct access to functionalized carbon nanomaterials. In this article, we present a synthetic approach that allows us to prepare hexayne carboxylate amphiphiles as carbon-rich siblings of typical fatty acid esters through a series of repeated bromination and Negishi-type crosscoupling reactions. The obtained compounds are designed to self-assemble into monolayers at the air-water interface, and we show how this can be achieved in a Langmuir trough. Thus, compression of the molecules at the air-water interface triggers the film formation and leads to a densely packed layer of the molecules. The complete carbonization of the films at the air-water interface is then accomplished by crosslinking of the hexayne layer at room temperature, using UV irradiation as a mild external stimulus. The changes in the layer during this process can be monitored with the help of infrared reflection-absorption spectroscopy and Brewster angle microscopy. Moreover, a transfer of the carbonized films onto solid substrates by the Langmuir-Blodgett technique has enabled us to prove that they were carbon nanosheets with lateral dimensions on the order of centimeters. Video LinkThe video component of this article can be found at

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“…Yet if the group itself is not directly ionized and is not in proximity of the suspected site of ionization, it may be preserved. Azidecontaining analytes (compounds [34][35][36], are a good illustration of this hypothesis. Typically, azides show strong [M+H -N 2 ] + loss [45], as well as, occasionally, loss of N 3 species (see APPI mass spectrum of compound 35 in Supplementary Figure S2).…”

Section: Reactive Functional Groupsmentioning

confidence: 99%

A Functional Group Approach for Prediction of APPI Response of Organic Synthetic Targets

Zhurov

Menin

Franco

et al. 2015

J. Am. Soc. Mass Spectrom.

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Abstract. Atmospheric pressure photoionization (APPI) is a technique of choice for ionization of non-polar molecules in mass spectrometry (MS). Reported APPI-based studies tend to focus on a selected compound class, which may contain a variety of functional groups. These studies demonstrate that APPI response frequently differs substantially, indicating a certain dependence on the functional group present. Although this dependence could be employed for APPI response prediction, its systematic use is currently absent. Here, we apply APPI MS to a judiciously-compiled set of 63 compounds containing a number of diverse functional groups commonly utilized in synthesis, reactive functional groups, as well as those containing boron and silicon. Based on the outcome of APPI MS of these compounds, we propose and evaluate a simple guideline to estimate the APPI response for a novel compound, the key properties of which have not been characterized in the gas phase. Briefly, we first identify key functional groups in the compound and gather knowledge on the known ionization energies from the smallest analogues containing said functional groups. We then consider local inductive and resonance effects on said ionization energies for the compounds of interest to estimate the APPI response. Finally, application of APPI MS to compounds of interest considered herein demonstrated extended upper mass ionization limit of 3.5 kDa for non-polymeric compounds.

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Facile synthesis of oligoyne amphiphiles and their rotaxanes

Abstract: Carbon-rich organic compounds containing a series of conjugated triple bonds (oligoynes) are relevant synthetic targets, but an improved access to oligoynes bearing functional groups would be desirable.

Cited by 60 publications

References 69 publications

Solvent Dependence of the Single Molecule Conductance of Oligoyne-Based Molecular Wires

Solvent Dependence of the Single Molecule Conductance of Oligoyne-Based Molecular Wires

Preparation of Carbon Nanosheets at Room Temperature

A Functional Group Approach for Prediction of APPI Response of Organic Synthetic Targets

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