Synthesis of Functionalized Triazatriangulenes for Application in Photo‐Switchable Self‐Assembled Monolayers

Kubitschke, Jens; Näther, Christian; Herges, Rainer

doi:10.1002/ejoc.201000650

Cited by 41 publications

(69 citation statements)

References 43 publications

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“…The aqueous layer was extracted with Et 2 O (4 ϫ 150 mL) and the combined organic layers were dried with MgSO 4 . The solvent was removed under reduced pressure and the crude product was purified by column chromatography (silica gel, n-pentane/DCM, 2:1) to afford a white solid (7,914 (5): (95.5 mg, 370 μmol) was dissolved in 50 mL dry THF and mixed with powdered KOH (140 mg, 2.50 mmol) and octyl TATA (11) (290 mg, 411 μmol). The mixture was stirred for 18 h under reflux.…”

Section: -(4-iodo-2-nitrobenzyl)-7-nitro-23-dihydro-1h-indene (7)mentioning

confidence: 99%

Diazocines on Molecular Platforms

2014

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Section: -(4-iodo-2-nitrobenzyl)-7-nitro-23-dihydro-1h-indene (7)mentioning

confidence: 99%

Diazocines on Molecular Platforms

2014

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“…Under an argon atmosphere, to a solution of compound 2 [19] (319 mg, 1.14 mmol) in dry THF (5 mL) were added K2CO3 (79 mg, 0.57 mmol) and MeOH (5 mL) and the reaction mixture was stirred for 2 h at room temperature. The resultant mixture was diluted with AcOEt (30 mL) and washed with H2O, followed by brine.…”

Section: Preparation Of 4-(4-ethynylphenylazo)pyridine (5)mentioning

confidence: 99%

“…4-4-[(Trimethylsilyl)ethynylphenylazo]pyridine 2 was synthesized from the prepared 4-(4-iodophenylazo)pyridine 1 [18] through a palladium-catalyzed cross-coupling reaction [22] with trimethylsilylacetylene. TMS-protected ethynyl-azobenzene derivatives 2-4 [19] were converted to compounds 5-7 by removal of the silyl group. Compounds 8 and 9 were also synthesized according to the reported procedures [20,21].…”

Section: Synthesis Of Para-substituted Du Az Phosphoramidites and Modmentioning

confidence: 99%

Synthesis and Properties of 2'-Deoxyuridine Analogues Bearing Various Azobenzene Derivatives at the C5 Position

et al. 2015

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Nucleic acids that change their properties upon photo-irradiation could be powerful materials for molecular sensing with high spatiotemporal resolution. Recently, we reported a photo-isomeric nucleoside bearing azobenzene at the C5 position of 2'-deoxyuridine (dU Az ), whose hybridization ability could be reversibly controlled by the appropriate wavelength of light. In this paper, we synthesized and evaluated dU Az analogues that have various para-substitutions on the azobenzene moiety. Spectroscopic measurements and HPLC analyses revealed that the para-substitutions of the azobenzene moiety strongly affect the photo-isomerization ability and thermal stability of the cis-form. The results suggest that proper substitution of the azobenzene moiety can improve the properties of dU Az as a light-responsive nucleic acid probe.

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“…1 We recently introduced the platform approach for preparation of wellordered adlayers with freestanding functional groups on metal surfaces and illustrated its feasibility by employing derivatives of the triazatriangulenium (TATA) ion. [2][3][4][5] The triangularshaped TATA platform can be functionalized either vertically at the central carbon or laterally at the outer nitrogen atoms and thus serves as a chemically very modular and versatile template. Up to now, more than 30 TATA derivatives with different functional groups have been synthesized.…”

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“…1), which were synthesized as described in the literature. The ionic species (TOTA and DEA 3 -TOTA) were synthesized as BF 4 À salts. All compounds were characterized by NMR and mass spectroscopy and have a purity of 499%.…”

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Adlayers based on molecular platforms of trioxatriangulenium

et al. 2011

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The platform approach for preparation of molecular adlayers with freestanding functional groups was extended to systems on the basis of the trioxatriangulenium ion. Self-assembled monolayers of these compounds were prepared on Au(111) surfaces and characterized by scanning tunneling microscopy, revealing highly-ordered structures.Organic surface functionalization with defined vertical architecture is of considerable current interest. 1 We recently introduced the platform approach for preparation of wellordered adlayers with freestanding functional groups on metal surfaces and illustrated its feasibility by employing derivatives of the triazatriangulenium (TATA) ion.2-5 The triangularshaped TATA platform can be functionalized either vertically at the central carbon or laterally at the outer nitrogen atoms and thus serves as a chemically very modular and versatile template. Up to now, more than 30 TATA derivatives with different functional groups have been synthesized. 4 Adlayers of these compounds have been studied by STM, 2,3,5 different spectroscopies, 5 and electrochemical methods. 5,3 Using these techniques the TATA derivatives were shown to form hexagonally-ordered adlayers where the platforms adsorb flat on the metal substrate, the intermolecular distances can be varied by the attached side groups, and the central functional groups are oriented perpendicularly to the surface. Although this approach turned out to be an excellent method for preparation of highly-ordered functional adlayers, the employed TATA platforms have some disadvantages. First, it is not possible to prepare functional TATA adlayers by vacuum deposition, because they decompose below their sublimation point. This limits their applicability for studies under ultrahigh vacuum conditions. Second, the inevitably present side groups attached to the nitrogen atoms partially reside above the TATA layer and (for the employed alkane chains) do not seem to exhibit well-defined positions, which reduces the structural order in the adlayers.In this work we use an alternative molecular platform system, derivatives of the trioxatriangulenium (TOTA) ion (Fig. 1), which does not have these disadvantages. TOTA is structurally closely related to TATA, but exhibits three oxygen atoms in the platform instead of nitrogen atoms with attached side groups and thus a significantly reduced molecular mass. Similarly as for TATA perpendicular as well as lateral functionalization is possible, although the latter only at para or meta positions of the benzene rings in the platform. The bond strength of vertically attached functional groups to the central carbon atom of the TOTA platform should be increased as compared to TATA, making these molecules better suited for adlayer preparation via vacuum deposition. The TOTA derivatives have been extensively studied since the 1960s, [6][7][8] but up to now not in context of surface functionalization. As we will show in the following STM studies, highly-ordered adlayers of TOTA and functional TOTA derivatives can be prepared on ...

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Synthesis of Functionalized Triazatriangulenes for Application in Photo‐Switchable Self‐Assembled Monolayers

Cited by 41 publications

References 43 publications

Diazocines on Molecular Platforms

Diazocines on Molecular Platforms

Synthesis and Properties of 2'-Deoxyuridine Analogues Bearing Various Azobenzene Derivatives at the C5 Position

Adlayers based on molecular platforms of trioxatriangulenium

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