Syntheses and electronic properties of the nickel and palladium complexes of the octaethylporphyrin(M1)–(dihexylbithiophene) n –octaethylporphyrin(M2) system [OEP(M1)–(DHBTh) n –OEP(M2)] connected with the diacetylene linkage. A methodology for molecular design of the particular electronic structure

Hayashi, Naoto; M, Murayama; Mori, Kazumine; Matsuda, Akihito; Chikamatsu, Emiko; Tani, Keita; Miyabayashi, Keiko; Miyake, Mikio; Higuchi, Hiroyoshi

doi:10.1016/j.tet.2004.04.064

Cited by 22 publications

(5 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The Ni(OEP) and Ni(meso-formyl-OEP) derivatives of H 2 (OEP) were prepared according to literature procedures . Ni(meso-ethynyl-OEP) and Cu(meso-ethynyl-OEP) 2 were prepared according to ref from a mixture of the corresponding meso-E/Z-2-chloroethenyl-OEP-compounds instead of the bromoethenyl derivatives (see Supporting Information) and used as obtained due to the products susceptibility to spontaneous oxidative dimerization …”

Section: Methodsmentioning

confidence: 99%

PELDOR Measurements on a Nitroxide-Labeled Cu(II) Porphyrin: Orientation Selection, Spin-Density Distribution, and Conformational Flexibility

et al. 2008

View full text Add to dashboard Cite

Metal ions are functionally or structurally important centers in metalloproteins or RNAs, which makes them interesting targets for spectroscopic investigations. In combination with site-directed spin labeling, pulsed electron-electron double resonance (PELDOR or DEER) could be a well-suited method to characterize and localize them. Here, we report on the synthesis, full characterization, and PELDOR study of a copper(II) porphyrin/nitroxide model system. The X-band PELDOR time traces contain besides the distance information a convolution of orientational selectivity, conformational flexibility, exchange coupling, and spin density distribution, which can be deconvoluted by experiments with different frequency offsets and simulations. The simulations are based on the known experimental and spin Hamiltonian parameters and make use of a geometric model as employed for structurally similar bis-nitroxides and spin density parameters as obtained from density functional theory calculations. It is found that orientation selection with respect to dipolar angles is only weakly resolvable at X-band frequencies due to the large nitrogen hyperfine coupling of the copper porphyrin. On the other hand, the PELDOR time traces reveal a much faster oscillation damping than observed for structurally similar bis-nitroxides, which is mainly assigned to a small distribution in exchange couplings J. Taking the effects of orientation selectivity, distribution in J, and spin density distribution into account leads finally to a narrow distance distribution caused solely by the flexibility of the structure, which is in agreement with distributions from known bis-nitroxides of similar structure. Thus, X-band PELDOR measurements at different frequency offsets in combination with explicit time trace simulations allow for distinguishing between structural models and quantitative interpretation of copper-nitroxide PELDOR data gives access to localization of copper(II) ions.

show abstract

Section: Methodsmentioning

confidence: 99%

PELDOR Measurements on a Nitroxide-Labeled Cu(II) Porphyrin: Orientation Selection, Spin-Density Distribution, and Conformational Flexibility

et al. 2008

View full text Add to dashboard Cite

show abstract

“…Deprotection with K 2 CO 3 and final coupling with octaethylporphyrin-Pd acetylene were followed by an Eglinton-type coupling. 333,334 The 1 H NMR spectral data revealed that all the triads possessed fairly simple skeletal features. IR spectral measurements demonstrated that the diethynylene linkage for the tail-to-tail series contributed more efficiently to an extension of the resonance structure with the porphyrin and dihexylbithiophene units, regardless of the number of bithiophene units.…”

Section: Porphyrin-functionalized Oligothiophenesmentioning

confidence: 99%

“…The syntheses of unsymmetrical Pd−Ni mixed-metal complexes of 2.246 ( n = 1) and 2.247 ( n = 1) were carried out by coupling octaethylporphyrin-Ni acetylene and a 5-bromo-5′-ethynylbithiophene precursor followed by a second Sonogashira coupling with trimethylsilyl acetylene. Deprotection with K 2 CO 3 and final coupling with octaethylporphyrin-Pd acetylene were followed by an Eglinton-type coupling. , The 1 H NMR spectral data revealed that all the triads possessed fairly simple skeletal features. IR spectral measurements demonstrated that the diethynylene linkage for the tail-to-tail series contributed more efficiently to an extension of the resonance structure with the porphyrin and dihexylbithiophene units, regardless of the number of bithiophene units.…”

Section: Functionalized Linear Oligothiophenesmentioning

confidence: 99%

Functional Oligothiophenes: Molecular Design for Multidimensional Nanoarchitectures and Their Applications

2009

View full text Add to dashboard Cite

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...

show abstract

“…1-Oxyl-2,2,5,5-tetramethylpyrrolin-3-acetylene (TPA) 4 [29] and 3-(4 0 -Iodo-biphenyl-4-ylethynyl)-2,2,5,5-tetramethylpyrrolin-1-oxyl 5 [10] were prepared by procedures described earlier. Cu(meso-ethynyl-OEP) 6 and Ni(meso-ethynyl-OEP) 7 were prepared according to references [16,30] and used as obtained, due to the products susceptibility to spontaneous oxidative dimerisation [31].…”

Section: Synthesismentioning

confidence: 99%