Expanded Radialenes: Modular Synthesis and Characterization of Cross-Conjugated Enyne Macrocycles

Eisler, Sara; Tykwinski, Rik R.

doi:10.1002/(sici)1521-3773(19990712)38:13/14<1940::aid-anie1940>3.0.co;2-8

Cited by 58 publications

(50 citation statements)

References 8 publications

(12 reference statements)

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“…64 The adamantylidene series of iso-PDAs (68) was made, and while kinetic stability was improved versus that of 62-67, solubility remained a serious issue. 63 The most successfully studied iso-PDAs have been the perphenylated derivatives 69.…”

Section: Iso-polydiacetylenesmentioning

confidence: 99%

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Oligomeric and Polymeric Systems with a Cross-conjugated π-Framework

2006

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Section: Iso-polydiacetylenesmentioning

confidence: 99%

“…64 The synthesis of 208 derived from the Sonogashira cross-coupling reaction of iso-PDA pentamer 67 with a dibromoolefin. Compound 209 was also formed as a result of oxidative homocoupling of the iso-polydiacetylene moiety.…”

Section: Expanded Radialenes With Acetylene Spacersmentioning

confidence: 99%

Oligomeric and Polymeric Systems with a Cross-conjugated π-Framework

2006

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“…Ever since the pioneering work by Sondheimer [37,38], acetylenic macrocycles continue to be studied both experimentally and theoretically to further enhance the understanding of aromaticity/antiaromaticity and π-conjugation in unsaturated macrocyclic systems [5,[39][40][41][42][43][44][45][46][47]. 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].…”

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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“…Shape-persistent, conjugated macrocycles with all-carbon skeletons are of interest to many research groups [53][54][55][56][57][58][59][60][61][62][63][64]. In our research aimed at producing large all-carbon sheets [7], we have become interested in three classes of macrocycles, perethynylated dehydroannulenes [65], perethynylated expanded radialenes [66], and perethynylated radiaannulenes [68].…”

Section: Large All-carbon Sheets With Peripheral Donor Groupsmentioning

confidence: 99%

“…In 1993, we had reported the first examples of the expanded radialenes [71] and had since then continued investigating the opto-electronic properties of these novel macrocyclic chromophores [72] (for other work, see [54,55]). In continuation of this work, three series of perethynylated expanded [n]radialenes (n = 3, 4, 6, 8) 8a-c, 9a-d, and 10a-d with differently functionalized peripheral phenyl rings were prepared and subjected to comprehensive physical-organic study (Fig.…”

Section: F Diederichmentioning

confidence: 99%

Advanced opto-electronics materials by fullerene and acetylene scaffolding

Diederich

2005

Pure and Applied Chemistry

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Functional π-systems with unusual opto-electronic properties are intensively investigated from both fundamental research and technological application viewpoints. This article reports on novel π-conjugated systems obtained by acetylenic and fullerene scaffolding. Linearly conjugated acetylenic nanorods, consisting of monodisperse poly(triacetylene) (PTA) oligomers and extending up to 18 nm length, were prepared to investigate the limits of effective conjugation and to explore at which length a monodisperse oligomer reaches the properties of an infinite polydisperse polymer. With the cyanoethynylethenes (CEEs), a powerful new class of electron acceptors is introduced that undergo intense intramolecular charge-transfer (CT) interactions with appended donors. Macrocyclic scaffolds with unusual opto-electronic properties are perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes bearing peripheral dialkylanilino donor groups. Extended porphyrin-fullerene conjugates are investigated for their novel photophysical and efficient multicharge storage properties. Self-assembly of fullerenes and porphyrins, governed by weak interactions between the two components, leads to unprecedented nanopatterned surfaces that are investigated by scanning tunneling microscopy (STM).

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Expanded Radialenes: Modular Synthesis and Characterization of Cross-Conjugated Enyne Macrocycles

Cited by 58 publications

References 8 publications

Oligomeric and Polymeric Systems with a Cross-conjugated π-Framework

Oligomeric and Polymeric Systems with a Cross-conjugated π-Framework

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

Advanced opto-electronics materials by fullerene and acetylene scaffolding

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