5,8,17,20-Tetrakis(3,5-di-<i>t</i>-butylphenyl)-6,7,18,19-tetradehydrotetrathia[24]annulene-(4.0.4.0) and Its Dianion: New Thiophene-Derived Paratropic and Diatropic Annulenes

Kurata, Hiroyuki; Baba, Hiroshige; Oda, Masaji

doi:10.1246/cl.1997.571

Cited by 13 publications

(8 citation statements)

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“…The sp‐hybridized carbon atoms of intermediate 7 gave a 13 C NMR signal at δ =84.4 ppm, that is, in the δ =70–95 ppm range typical for acetylene. Similarly, the 13 C NMR chemical shifts of cumulene fragments vary over quite a wide range: δ =140.5 ppm for tetra(2‐thienyl)butatriene,11 δ =152.0 ppm for tetraphenylbutatriene,12 and δ =134.5 ppm for 6,7,18,19‐tetradehydrotetrathia[24]annulene(4.0.4.0) (some admixture of the acetylenic structure was suggested for the latter structure) 13. Thus the 13 C NMR chemical shifts of 3 point out that canonical structure 3 ac and 3 cum (ac=acetylene; cum=cumulene) contribute to the overall electronic structure, although the acetylene character of the C sp –C sp moiety prevails.…”

Section: Methodsmentioning

confidence: 99%

“…The structure of 3 was determined by X‐ray diffraction studies and is shown in Figure 3 17. The S⋅⋅⋅S distance is short (3.113(3) Å), and only a small number of compounds that contain such close sulfur–sulfur contacts have been reported 13. 18–20 The C

_{sp^{2}}

‐C sp ‐C sp ‐C

_{sp^{2}}

butyne moiety reveals a slight distortion from linearity, showing a bowlike deformation directed outward of the macrocycle (C18‐C1‐C2: 174.0(9)°; C1‐C2‐C3: 176.6(9)°).…”

Section: Methodsmentioning

confidence: 99%

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Dithiaethyneporphyrin: An Atypical [18]Triphyrin(4.1.1) Frame for Contracted Porphyrins

2005

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Section: Methodsmentioning

confidence: 99%

_{sp^{2}}

‐C sp ‐C sp ‐C

_{sp^{2}}

butyne moiety reveals a slight distortion from linearity, showing a bowlike deformation directed outward of the macrocycle (C18‐C1‐C2: 174.0(9)°; C1‐C2‐C3: 176.6(9)°).…”

Section: Methodsmentioning

confidence: 99%

Dithiaethyneporphyrin: An Atypical [18]Triphyrin(4.1.1) Frame for Contracted Porphyrins

2005

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“…The macrocycle showed clear paratropicity (antiaromaticity) whereas the dianion, a 26π electron system which is obtained by alkali reduction, was strongly diatropic (aromatic). 670 Macrocyclization Via McMurry coupling was very recently used by Iyoda et al to synthesize large thienylene-ethynylene-vinylene macrocycles 4.54 in a statistical approach. 671 Reaction of a longer oligo(thienylene-ethynylene) dialdehyde, which was made from thiophene in 12 steps, with TiCl 4 and zinc resulted in a statistical distribution of macrocycles with various sizes (Scheme 4.19).…”

Section: Mixed Macrocycles Including R-substitution In Thiophene Unitsmentioning

confidence: 99%

Functional Oligothiophenes: Molecular Design for Multidimensional Nanoarchitectures and Their Applications

2009

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Amaresh Mishra (right) received his Ph.D. degree in 2000 from the Sambalpur University, India, under the coguidance of Prof. G. B. Behera and Prof. R. K. Behera, working on dye-surfactant interactions in microheterogeneous media. He started his postdoctoral research career in 1999 at the University of South Florida, Tampa, and subsequently at the University of Akron, Ohio, working with Prof. G. R. Newkome, where he gained knowledge in the area of supramolecular and dendrimer chemistry. Later, he joined the Tata Institute of Fundamental Research, Mumbai, in 2002 as a Visiting Fellow working with Prof. N. Periasamy, where he was involved in the synthesis and photophysical studies of organic light emitting materials. In 2005, he joined in the group of Prof. Peter Ba ¨uerle, University of Ulm, Germany, as an Alexander von Humboldt Fellow. His present research interests are centered on chemistry of functional oligothiophenes, donor-acceptor-based conjugated dyes, and metal complexes toward applications in solar energy conversion and molecular electronic and photonic devices. Chang-Qi Ma (left) received his bachelor's degree in chemistry from Beijing Normal University in 1998. In 2003 he obtained his Ph.D. degree at the Technical Institute of Physics and Chemistry, Chinese Academy of Sciences in Beijing with Professor B.-W. Zhang. After that he was a postdoctoral research assistant at Heriot-Watt University in Edinburgh, U.K., with Dr. G. Cooke, until he joined the research group of Prof. P. Ba ¨uerle at the University of Ulm in 2004 as an Alexander von Humboldt fellow, where he is currently a research associate. His main research interests focus on the design and synthesis of novel π-conjugated organic materials for the application in organic electronics, e.g. organic solar cells.Peter Ba ¨uerle (center) received his Ph.D. in organic chemistry from University of Stuttgart (Germany, 1985) working with Prof. F. Effenberger. After a postdoctoral year at MIT, Boston, Massachusetts, in the group of Prof. M. S. Wrighton, he carried out independent research at the University of Stuttgart and received his habilitation (1994). After being Professor of Organic Chemistry at the University of Wu ¨rzburg (Germany, 1994-95), he became Director of the Institute for Organic Chemistry II and Advanced Materials at the University of Ulm (Germany, since 1996). Current research interests of the group include development of novel organic semiconducting and conducting materials, in particular, conjugated poly-and oligothiophenes. Synthetic strategies and new reactions for their functionalization, structure-property relationships, self-assembling properties, and applications in electronic devices, in particular organic solar cells, are investigated. Results have been published in about 200 peer-reviewed scientific papers, 3 book chapters, and 7 patents. For his work in the field of plastic electronics he was awarded with the Rene ´Descartes Prize of the European Union (2000). Guest Professorships at the University of Osaka (Japan, 2002), U...

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“…Incorporation of an acetylene–cumulene unit into a porphyrinoid skeleton provides the unique means to design a molecular frame affording eventually effective control of the electronic structure that encloses the π-conjugation pathway of aromatic molecules. Originally, the annulene–cumulene moieties have been successfully embedded into porphyrinoids, heteroporphyrinoids, or expanded porphyrinoids, furnishing the specific subgroup of expanded porphyrinoids, − the representative examples of which include acetylene–cumulene porphycene 1 (Chart ) …”

Section: Introductionmentioning

confidence: 99%

Nickel(II) and Palladium(II) Thiaethyneporphyrins. Intramolecular Metal(II)−η²-CC Interaction inside a Porphyrinoid Frame

et al. 2012

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3,18-Diphenyl-8,13-di-p-tolyl-20-thiaethyneporphyrin ([18]thiatriphyrin(4.1.1)), which formally contains an C1-C2 ethyne moiety instead of pyrrole embedded in the macrocyclic framework of 21-thiaporphyrin, was obtained in a modification of the "3 + 1" approach using the ethyne analogue of tripyrrane (1,4-diphenyl-1,4-di(pyrrol-2-yl)but-2-yne) and 2,5-bis(p-tolylhydroxymethyl)thiophene. The spectroscopic and structural properties of 20-thiaethyneporphyrin reflect its macrocyclic aromaticity, revealing a combination of the acetylene (≥C-C≡C-C≤) and cumulene (>C═C═C═C<) character of the C18-C1-C2-C3 linker. The magnetic manifestations of aromaticity and antiaromaticity of thiaethyneporphyrin and its two-electron-oxidized derivative were observed using (1)H NMR spectroscopy and were confirmed by density functional theory calculations involving chemical shifts and nucleus-independent chemical shift analysis. Protonation of 20-thiaethyneporphyrin yielded a nonaromatic tautomer of iso-20-thiaethyneporphyrin, locating the saturated meso carbon adjacent to thiophene. Insertion of palladium(II) and nickel(II) into 20-thiaethyneporphyrin afforded planar palladium(II) thiaethyneporphyrin and low-spin diamagnetic nickel(II) 20-thiaethyneporphyrin as determined by X-ray crystallography. 20-Thiaethyneporphyrin acts as a dianionic ligand that coordinates through the two nitrogen and one sulfur donors. Metal(II) ions are uniquely exposed to form an intramolecular metal(II)-η(2)-CC bond, whereas the organometallic fragment is coplanar with the whole macrocycle. Coordination of pyridine converts diamagnetic nickel(II) thiaethyneporphyrin into its paramagnetic counterpart as determined by (1)H NMR.

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5,8,17,20-Tetrakis(3,5-di-t-butylphenyl)-6,7,18,19-tetradehydrotetrathia[24]annulene-(4.0.4.0) and Its Dianion: New Thiophene-Derived Paratropic and Diatropic Annulenes

Cited by 13 publications

References 11 publications

Dithiaethyneporphyrin: An Atypical [18]Triphyrin(4.1.1) Frame for Contracted Porphyrins

Dithiaethyneporphyrin: An Atypical [18]Triphyrin(4.1.1) Frame for Contracted Porphyrins

Functional Oligothiophenes: Molecular Design for Multidimensional Nanoarchitectures and Their Applications

Nickel(II) and Palladium(II) Thiaethyneporphyrins. Intramolecular Metal(II)−η²-CC Interaction inside a Porphyrinoid Frame

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5,8,17,20-Tetrakis(3,5-di-t-butylphenyl)-6,7,18,19-tetradehydrotetrathia[24]annulene-(4.0.4.0) and Its Dianion: New Thiophene-Derived Paratropic and Diatropic Annulenes

Cited by 13 publications

References 11 publications

Dithiaethyneporphyrin: An Atypical [18]Triphyrin(4.1.1) Frame for Contracted Porphyrins

Dithiaethyneporphyrin: An Atypical [18]Triphyrin(4.1.1) Frame for Contracted Porphyrins

Functional Oligothiophenes: Molecular Design for Multidimensional Nanoarchitectures and Their Applications

Nickel(II) and Palladium(II) Thiaethyneporphyrins. Intramolecular Metal(II)−η2-CC Interaction inside a Porphyrinoid Frame

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Nickel(II) and Palladium(II) Thiaethyneporphyrins. Intramolecular Metal(II)−η²-CC Interaction inside a Porphyrinoid Frame