Synthesis and Properties of Oligo[<i>n</i>]cruciforms: Nanosized Sterically Encumbered Tetraethynylphenyl-Homologated Fluorophores

Ouahabi, Abdelaziz Al; Baxter, Paul N. W.; Gisselbrecht, Jean‐Paul; Cian, André De; Brelot, Lydia; Kyritsakas‐Gruber, Nathalie

doi:10.1021/jo802797e

Cited by 17 publications

(30 citation statements)

References 96 publications

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“…[58] Further studies have since been reported for [12]DBAs functionalized with CN, F, and COOMe acceptor, and NR 2 and OMe donor groups, [42,47] and [12]DBAs variously functionalized with ethynyl substituents. [13,59] In accordance with the conclusions from theoretical studies, [42] acceptor substituents facilitate reduction of the [12]DBA ring system relative to 1, while donor functionality enables oxidation processes to occur. Ethynyl substituents stabilize the [12]DBA ring to reduction relative to 1.…”

Section: Electrochemical Study Ofsupporting

confidence: 77%

A Direct One‐Pot Synthesis of Asymmetric Dehydrobenzopyrido[12]annulenes and Their Physicochemical Properties

et al. 2017

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A direct one‐pot synthesis of asymmetric dehydrobenzopyrido[12]annulenes 2 and 3 containing one or two pyridine rings is reported that employs a Stephens–Castro mediated cross‐coupling of mixtures of ethynylcuprate precursors. The spectroscopic and theoretical properties of 2 and 3 are compared to those of the threefold symmetric dehydrotribenzo[12]annulene 1, and dehydrotripyrido[12]annulenes 4 and 5 and dehydrodibenzodipyrido[16]annulene byproduct 6, and showed 1–5 to be essentially isoelectronic band gap materials whose electron accepting ability increases with increasing nitrogen incorporation. The structures of 2, 4 and 6 were also unambiguously characterized by X‐ray crystallography. The results highlight the potential dehydroaryl[12]annulenes incorporating pyridines offer for the construction of high carbon content electronic materials.

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Section: Electrochemical Study Ofsupporting

confidence: 77%

A Direct One‐Pot Synthesis of Asymmetric Dehydrobenzopyrido[12]annulenes and Their Physicochemical Properties

et al. 2017

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“…11 Arylalkynes are known to serve as intriguing building blocks for the covalent construction of molecular architectures. [12][13][14][15][16] The viability of interparticle linkages via coordination of the methylthio groups of V-, Y-, and X-shaped arylethynes to gold surfaces was demonstrated recently in our laboratory. 17, 18 However, a key challenge is to determine the interparticle properties of such interparticle assemblies mediated by shaped methylthio arylethynes (MTAs) for exploiting their unique optical and electrical properties.…”

Section: Introductionmentioning

confidence: 93%

Rigid, conjugated and shaped arylethynes as mediators for the assembly of gold nanoparticles

et al. 2011

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The ability to control and tailor the interparticle structures and properties of molecularly-mediated assembly of nanoparticles in terms of molecular size, shape, and structure is essential for exploring the nanostructured multifunctional properties. This report describes the results of an investigation on how such molecular size, shape, and structure are operative in the assembly of gold nanoparticles mediated by rigid methylthio arylethynes (MTAs) of different shapes (e.g., I, V, Y, and X shapes). The goal of this investigation focuses on understanding the correlation between the interparticle molecular structures and the optical and spectroscopic (e.g., surface-enhanced Raman scattering (SERS)) properties in this class of molecularly-mediated assembly of nanoparticles. The surface plasmon resonance bands of the nanoparticles, the electronic transition bands of the mediator molecules, the dynamic light scattering of the assembly processes, and the SERS signatures of the interparticle structures are systematically compared for a series of MTAs. Important insights have been gained into the relative binding strength of the different MTAs in the single-and two-component mediated assembly processes. The results have demonstrated that the interparticle spacing and structures of nanoparticle assemblies can be defined by these rigid and shaped molecules. This type of interparticle structural definition can be controlled to produce well-defined optical and spectroscopic signatures, which is especially important for understanding interparticle optical or spectroscopic characteristics (e.g., ''hot-spot'' in nanoparticle-based SERS effect). Implications of the findings to enabling the design of interparticle structure and the control of the interparticle properties in nanoparticle assembly systems for potential applications in chemical/bio sensing, spectroscopic signal amplification, and microelectronics are also briefly discussed.

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“…Subsequent de-silylation of 10 with [(nBu) 4 N]F in THF/H 2 O yielded 11, which was isolated in 91 % yield after workup. A further Sonogashira reaction of 11 and two equivalents of 12 [43] mediated by [PdCl 2 A C H T U N G T R E N N U N G (PPh 3 ) 2 ] and CuI as catalysts afforded 13 in 41 % yield. Longer reaction times facilitated higher yields of 13, although the overall moderate yields of the latter terpyridine were ascribed to extensive byproduct contamination.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of a Strained Acetylenic Macrocycle Incorporating a para‐Oligo[2]cruciform Bridge Bent over Nanoscopic Dimensions: Structural, Electronic, Spectroscopic, and Ion‐Sensing Properties

Baxter

Gisselbrecht

Karmazin-Brelot

et al. 2013

Chemistry A European J

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An Eglinton-Galbraith diethyne cyclization preferentially yielded a structurally unusual macrocycle, comprising a strained conjugated oligo[2]cruciform wire, forced into a 2.2 nm bow-shape by a terpyridine rein or tether, and stabilized towards light and heat by four insulating triisopropylsilylacetylene (TIPSA) substituents. Spectroscopic ion-binding studies revealed the macrocycle to exhibit a particularly high UV/Vis selectivity for Pd(II) in dilute solution, and one of its precursors to afford a variety of luminescence quenching and color responses to particular metals, suggestive of promising ion-sensor applications. Under more concentrated conditions, the new macrocycle is able to bind specific metals (e.g., Au(I)) within its cavity despite the steric constraints. Intriguingly, variable-temperature (VT) UV/Vis/(1)H NMR investigations showed the TIPSA substituents to undergo restricted intramolecular motions along with reversible changes in the spectroscopic bandgap of the compound with temperature. In line with the theoretical calculations, the VT UV/Vis observations are consistent with a thermal modulation of the electronic conjugation through the strained oligo[2]cruciform bridge, which is coupled with redistributions within a mixture of conformational isomers of the macrocycle with differing relative twisting between the TIPSA-substituted phenyl rings. Overall, the generation of a para-oligo[2]cruciform, bent and flexed over nanoscopic dimensions through conformational tethering within the macrocyclic ring is noteworthy, and suggests a general approach to nanosized, curved, and strained, yet heat- and light-stable, para-phenyleneethynylene oligomers with unique physicochemical properties and challenging theoretical possibilities.

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Synthesis and Properties of Oligo[n]cruciforms: Nanosized Sterically Encumbered Tetraethynylphenyl-Homologated Fluorophores

Cited by 17 publications

References 96 publications

A Direct One‐Pot Synthesis of Asymmetric Dehydrobenzopyrido[12]annulenes and Their Physicochemical Properties

A Direct One‐Pot Synthesis of Asymmetric Dehydrobenzopyrido[12]annulenes and Their Physicochemical Properties

Rigid, conjugated and shaped arylethynes as mediators for the assembly of gold nanoparticles

Synthesis of a Strained Acetylenic Macrocycle Incorporating a para‐Oligo[2]cruciform Bridge Bent over Nanoscopic Dimensions: Structural, Electronic, Spectroscopic, and Ion‐Sensing Properties

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