Donor-substituted peralkynylated “radiaannulenes”: novel all-carbon macrocycles with an intense intramolecular charge-transfer

Mitzel, Frieder; Boudon, Corinne; Gisselbrecht, Jean‐Paul; Seiler, Paul; Gross, Maurice; Diederich, François

doi:10.1039/b304130a

Cited by 34 publications

(27 citation statements)

References 8 publications

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“…5) were prepared, in some cases in excellent yield, by versatile acetylenic scaffolding using TEE building blocks. [88,108] Using cross-coupling reactions in the ultimate macrocycle-forming step, the bicyclic radiaannulene 27 has also recently become available. [98,99] X-ray crystal structures revealed for both 25a and 27 planar, strained cyclic all-carbon cores.…”

Section: Expanded Radialenes and Radiaannulenesmentioning

confidence: 99%

All‐Carbon Scaffolds by Rational Design

2010

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The search for new molecular and regular polymeric allotropes of carbon has greatly stimulated the preparation and investigation of pi-conjugated acetylenic macrocycles, which often represent substructures of proposed 2D carbon networks. Perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes with large, multi-nanometer-sized all-carbon cores are potent electron acceptors, and their optoelectronic as well as stability and solubility properties are greatly enhanced by peripheral donor substitution. Acetylenic scaffolding into three dimensions has generated an expanded cubane with a C(56) core, the first representative of a new class of "platonic" objects. Exceptional chiroptical properties displayed by enantiomerically pure alleno-acetylenic, shape-persistent macrocycles promise fascinating perspectives for the development of molecular and supramolecular chiroptical materials.

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Section: Expanded Radialenes and Radiaannulenesmentioning

confidence: 99%

All‐Carbon Scaffolds by Rational Design

2010

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“…Here, we report a new, simple photochemical route to (Z)-bisdeprotected TEEs that finally enabled the preparation and spectroscopic investigation of the perethynylated dehydroannulenes 5 and 6, which bear lateral N,Ndimethylanilino (DMA) substituents (for a preliminary communication of parts of this work, see [26]). We also report here the synthesis and properties of 7 ± 9, and 10 and 11, mono-and bicyclic members of a new family of all-C macrocycles, that, from a structural viewpoint, can be regarded as hybrids between the dehydroannulenes and expanded radialenes, and which we have, therefore, christened −radiaannulenes× (for a preliminary communication, see [27]). The intramolecular charge-transfer properties of the new donor-substituted all-C cores 5 ± 11 are discussed in detail.…”

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confidence: 97%

“…The compound crystallizes in the triclinic space group P1 ≈ with two molecules in the unit cell. The X-ray crystal structure [27] shows a virtually planar macrocyclic framework with a mean out-of-plane deviation of 0.040 ä and a maximum deviation of 0.091 ä (C(6); Fig. 2).…”

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Donor‐Substituted Perethynylated Dehydroannulenes and Radiaannulenes: Acetylenic Carbon Sheets Featuring Intense Intramolecular Charge Transfer

Mitzel

Boudon²,

Gisselbrecht³

et al. 2004

Helvetica Chimica Acta

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In this article, we report the preparation of unprecedented p-conjugated macrocycles (Fig. 1) by acetylenic scaffolding using modular tetraethynylethene (TEE, 3,4-diethynylhex-3-ene-1,5-diyne) building blocks. A novel photochemical access to (Z)-bisdeprotected TEEs (Scheme 1) enabled the synthesis of the anilino-substituted perethynylated octadehydro[12]-(5) and dodecadehydro [18]annulenes (6) (Scheme 2). Following the serendipitous discovery of perethynylated radiaannulenes (Scheme 3) that can be viewed as hybrids between perethynylated dehydroannulenes and expanded radialenes, two series of monocyclic (7 ± 9; Scheme 6) and bicyclic (10 and 11; Scheme 7) representatives were prepared. Substantial strain in the macrocyclic perimeter of radiaannulene 7 was revealed by X-ray crystal-structure analysis (Fig. 2). Nevertheless, mono-and bicyclic radiaannulenes are stable at room temperature in air for months. The opto-electronic properties of both dehydroannulenes and radiaannulenes are substantially enhanced by the introduction of the peripheral anilino donor groups that undergo strong intramolecular charge-transfer interactions with the electron-accepting all-C cores. As a result, the UV/VIS spectra feature intense, bathochromically shifted charge-transfer bands that disappear upon protonation of the anilino moieties and are fully recovered upon neutralization (Figs. 4 ± 9). A comparison between anilino-substituted perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes revealed that the efficiency of the intramolecular charge-transfer interaction strongly depends on the structure of the electron-accepting all-C perimeter. Electrochemical investigations (Table) demonstrated that the radiaannulenes are particularly powerful electron acceptors. Thus, bicyclic radiaannulene 11, which possesses eight peripheral 3,5-di(tert-butyl)phenyl substituents, is reversibly reduced at À 0.83 V in THF (vs. Fc / Fc), making it a better electron acceptor than buckminsterfullerene C 60 under comparable conditions.

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“…Over the past decade, we applied TEE building blocks to the construction of novel families of acetylenic macrocycles such as perethynylated dehydroannulenes [48][49][50][51], expanded radialenes [49,[52][53][54], and radiaannulenes combining the structural features of both dehydroannulenes and expanded radialenes [51,55]. With their extended π-chromophores, a number of representatives feature interesting optoelectronic properties, such as high third-order optical nonlinearities [53,54].…”

Section: Large Perethynylated Donor-substituted Carbon Sheetsmentioning

confidence: 99%

Conjugation and optoelectronic properties of acetylenic scaffolds and charge-transfer chromophores

Kivala

Diederich

2008

Pure and Applied Chemistry

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Our group started a research program in acetylene chemistry in 1987; since then, an intense research effort led to a fascinating journey into acetylenic scaffolding, aimed at exploring conjugative and optoelectronic properties of acetylenic chromophores. This journey included the generation of a unique molecular construction kit for acetylenic scaffolding, consisting of (E)-1,2-diethynylethenes [DEEs, (E)-hex-3-ene-1,5-diynes], tetraethynylethenes (TEEs, 3,4-diethynylhex-3-ene-1,5-diynes), chiral 1,3-diethynylallenes (DEAs, hepta-3,4-diene-1,6-diynes), 1,4-di and 1,1,4,4-tetraethynylbutatrienes, chiral trialkynylmethanes, and 1,1,2,2-tetraethynylethanes. These building modules were subsequently applied to the synthesis of carbon-rich architectures extending into one, two, and three dimensions. They include multinanometer-long monodisperse oligomers as models for infinite acetylenic polymers, molecular switches, perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes, and an octamethoxy-substituted expanded cubane with a central C 56 core. Donor-substituted cyanoethynylethenes (CEEs) and 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs) were introduced as new push-pull chromophores featuring intense intramolecular charge-transfer (CT) interactions. Dendritic multivalent CT chromophores were constructed using atom-economic, "click"-like reactions, and these systems were shown to behave as "molecular batteries", featuring exceptional electron uptake and storage capacity. The research finally led to the development of an unprecedented cascade reaction for the preparation of dendritic and oligomeric donor-acceptor (D-A) molecules. New [AB]-type oligomers become accessible in domino reactions involving repetitive sequences of [2+2] cycloadditions of tetracyanoethylene (TCNE) and tetrathiafulvalene (TTF) to polyynes, followed by retro-electrocyclizations.

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Donor-substituted peralkynylated “radiaannulenes”: novel all-carbon macrocycles with an intense intramolecular charge-transfer

Cited by 34 publications

References 8 publications

All‐Carbon Scaffolds by Rational Design

All‐Carbon Scaffolds by Rational Design

Donor‐Substituted Perethynylated Dehydroannulenes and Radiaannulenes: Acetylenic Carbon Sheets Featuring Intense Intramolecular Charge Transfer

Conjugation and optoelectronic properties of acetylenic scaffolds and charge-transfer chromophores

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