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61.
The synthesis and characterization of defined-length di- and trimeric pentacenes and the corresponding polymers are described. The synthesis is divergent from two common pentacene building blocks, 1 and 2, allowing for structural diversity. The resulting materials are air stable and exhibit good solubility in common organic solvents. 相似文献
62.
RikR. Tykwinski Anouk Hilger Franois Diederich HansPeter Lüthi Paul Seiler Volker Gramlich Jean‐Paul Gisselbrecht Corinne Boudon Maurice Gross 《Helvetica chimica acta》2000,83(7):1484-1508
Tetraethynylethenes (TEEs) functionalized with donor (4‐(dimethylamino)phenyl) and acceptor (5‐nitro‐2‐thienyl) groups were prepared by Pd0‐catalyzed Sonogashira cross‐coupling reactions (Schemes 1 – 6). The physical properties of these novel chromophores were examined and compared with those of analogous systems containing 4‐nitrophenyl instead of 5‐nitro‐2‐thienyl acceptor groups. X‐Ray crystal‐structure analyses showed the π‐conjugated frameworks of 2 , 11 , and 13 , including the TEE core and all aryl moieties, to be nearly perfectly planar (Figs. 1, 3, and 4). In contrast, one 4‐(dimethylamino)phenyl group in 10 is rotated almost 90° out of the molecular plane, presumably due to crystal‐packing effects (Fig. 2). The analysis of bond lengths and bond angles revealed little, if any, evidence of intramolecular ground‐state donor‐acceptor interactions. The electrochemical behavior of nitrothienyl‐substituted TEEs is similar to that of the corresponding nitrophenyl‐functionalized derivatives (Table 3). The nitrothienyl groups were reduced at −1.23 V (vs. the ferrocene/ferricinium couple, Fc/Fc+), regardless of the degree or pattern of other substitutions. For nonsymmetrical TEE 13 , the reduction of the nitrothienyl group at −1.23 V is followed by a reduction of the nitrophenyl group at −1.40 V, a potential typical for the reduction of other nitrophenyl‐substituted TEEs, such as 17 – 20 . UV/VIS Spectroscopy showed a consistently lower‐energy absorption cutoff for nitrothienyl derivatives compared with the analogous nitrophenyl‐substituted TEEs that confirms a lowering of the HOMO‐LUMO gap as a result of nitrothiophene substitution (Figs. 5 and 6). A comparison of the tetrakis‐arylated TEEs 11 , 13 , and 20 clearly showed a steady bathochromic shift of the longest‐wavelength absorption maximum and the end‐absorption upon sequential replacement of nitrophenyl by nitrothienyl groups. Quantum‐chemical computations were performed to explain a number of complex features of the electronic absorption spectra. All empirical features of relevance in the experimental UV/VIS spectra for 2 , 5 , 6 , and 17 – 19 were correctly reproduced by computation (Tables 4 and 5). The combination of theory and experiment was found to be very useful to explain the particular acceptor properties of the 5‐nitro‐2‐thienyl group. 相似文献
63.
Andrea Lucotti Matteo Tommasini Wesley A. Chalifoux Daniele Fazzi Giuseppe Zerbi Rik R. Tykwinski 《Journal of Raman spectroscopy : JRS》2012,43(1):95-101
Infrared (IR) and Raman spectroscopy have been used to examine the vibrational characteristics of a series of three macrocyclic tetraynes in comparison with an acyclic analog. By changing the length of the alkyl tether of the macrocycles, varying degrees of bending of the tetrayne moiety can be achieved, and the joint use of IR and Raman spectroscopies provides an avenue to probe the impact of bending on the sp‐chain. The spectroscopic data show a general trend toward decreasing activation of Raman bands in the IR spectra, and vice versa, as bending of the polyyne chain is decreased. Density functional theory calculations provide a detailed rationalization of the experimental observations. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
64.
Movsisyan LD Kondratuk DV Franz M Thompson AL Tykwinski RR Anderson HL 《Organic letters》2012,14(13):3424-3426
Active-metal templating has been used to synthesize rotaxanes consisting of a phenanthroline-based macrocycle threaded around a C8, C12, or C20 polyyne chain. The crystal structure of the C12 rotaxane has been determined. In the rhenium(I) carbonyl complex of this rotaxane, with Re(CO)(3)Cl coordinated to the phenanthroline macrocycle, the proximity of the polyyne chain quenches the luminescence of the rhenium. These rotaxanes offer a new approach to controlling the environment and interactions of a polyyne chain. 相似文献
65.
Synthesis and Aggregation Behavior of Chiral Naphthoquinoline Petroporphyrin Asphaltene Model Compounds 下载免费PDF全文
Matthias Schulze Dr. Alexander Scherer Dr. Frank Hampel Prof. Jeffrey M. Stryker Prof. Rik R. Tykwinski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3378-3386
The synthesis of structurally relevant compounds that model the chemical behavior and supramolecular aggregation of the asphaltenes, the most polar and metal‐rich fraction of heavy petroleum, has been extended to include fusions of important petroleum biomarkers. The synthetic protocol features a multicomponent reaction to form a dyad composed of a fused steroidal naphthoquinoline, followed by a pyrrole cyclocondensation reaction to incorporate the dyad into a chiral triad containing a NiII‐porphyrin substituent. This synthetic protocol has been used to prepare large molecules that represent both “continental” and “archipelago” models of asphaltene composition. The steroid–naphthoquinoline–porphyrin triads have been studied by UV/Vis and circular dichroism (CD) spectroscopies, and the results suggest that the naphthoquinoline core, a tetrahydro[4]helicene, adopts a helical conformation, producing a CD signal electronically related to the characteristic Soret absorption band of the porphyrin subunit. Finally, supramolecular aspects of asphaltene aggregation have been examined on a molecular level through analysis of axial coordination of pyridine to the Ni‐porphyrin. The relative affinity of pyridine for binding to the Ni center of the porphyrin is evaluated by comparing binding propensities in a series of sterically differentiated substituted porphyrins. 相似文献
66.
Yildizhan MM Fazzi D Milani A Brambilla L Del Zoppo M Chalifoux WA Tykwinski RR Zerbi G 《The Journal of chemical physics》2011,134(12):124512
The infrared (IR) spectrum of an adamantyl endcapped α, ω-polyyne (the hexayne, Ad-C(12)-Ad) is investigated both experimentally and computationally. A new IR band is observed upon UV photoexcitation of the compound (embedded in a poly methyl methacrylate matrix at 78 K), thus, revealing the existence of new photogenerated molecular structure trapped at low temperature. Complete reversibility is found, thus, demonstrating that the photoexcitation is responsible for the generation of metastable excited states of the molecule. Density functional theory and time dependent density functional theory calculations indicate that these metastable states result from the forbidden singlet (S(1)) or triplet (T(1)) excited states, and geometry optimizations of the polyyne trapped in either S(1) and/or T(1) states demonstrate that the carbon chain takes on a cumulenic structure. Comparison of the experimental and the computed IR spectra for the molecule trapped in the forbidden states confirms that the new IR features are clear markers of cumulenic species. The temperature and time dependent behavior of the new IR band is analyzed, while the experimentally determined value of the activation energy highlights the low stability of these molecular structures. 相似文献
67.
Owen BC Gao J Borton DJ Amundson LM Archibold EF Tan X Azyat K Tykwinski R Gray M Kenttämaa HI 《Rapid communications in mass spectrometry : RCM》2011,25(14):1924-1928
While atmospheric pressure ionization methodologies have revolutionized the mass spectrometric analysis of nonvolatile analytes, limitations native to the chemistry of these methodologies hinder or entirely inhibit the analysis of certain analytes, specifically, many nonpolar compounds. Examination of various analytes, including asphaltene and lignin model compounds as well as saturated hydrocarbons, demonstrates that atmospheric pressure chemical ionization (APCI) using CS2 as the reagent produces an abundant and stable molecular ion (M+?) for all model compounds studied, with the exception of completely saturated aliphatic hydrocarbons and the two amino acids tested, arginine and phenylalanine. This reagent substantially broadens the applicability of mass spectrometry to nonvolatile nonpolar analytes and also facilitates the examination of radical cation chemistry by mass spectrometry. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
68.
Optically Pure,Monodisperse cis‐Oligodiacetylenes: Aggregation‐Induced Chirality Enhancement 下载免费PDF全文
Dr. Erin T. Chernick Dr. Gabor Börzsönyi Christian Steiner Maximilian Ammon David Gessner Sabine Frühbeißer Prof. Dr. Franziska Gröhn Prof. Dr. Sabine Maier Prof. Dr. Rik R. Tykwinski 《Angewandte Chemie (International ed. in English)》2014,53(1):310-314
Conformational changes in the conjugated backbone of poly‐ and oligodiacetylenes (PDAs and ODAs) play an important role in determining the electronic properties of these compounds. At the same time, conformational changes can also result in a folded structure that shows helical chirality. Using D ‐camphor as a chiral building block, we have designed a high‐yielding, iterative synthesis of monodisperse, optically pure cis‐oligodiacetylenes (ODAs). cis‐ODAs up to the tridecamer have been formed, which is the longest monodisperse cis‐ODA reported to date. UV/Vis spectroscopy suggests a large effective conjugation length in THF, likely the result of a linear, planar conformation in this solvent. High‐resolution STM/AFM measurements of the nonamer cast from THF onto HOPG show a linear structure. In iPrOH, circular dichroism (CD) spectra suggest the formation of chiral aggregates for ODAs with at least nine D ‐camphor units, based on a strong CD response. 相似文献
69.
Renata Monteiro-Maia Maria B Ortig?o-de-Sampaio Rosa T Pinho Luiz RR Castello-Branco 《Journal of immune based therapies and vaccines》2006,4(1):4
Background
Oral administration of BCG was the route initially used by Calmette and Guérin, but was replaced by intradermal administration in virtually all countries after the Lubeck accident. However, Brazil continued to administer oral BCG Moreau RDJ, which was maintained until the mid-1970s when it was substituted by the intradermal route. Although BCG vaccination has been used in humans since 1921, little is known of the induced immune response. The aim of this study was to analyse immunological responses after oral vaccination with M. bovis BCG Moreau RDJ. 相似文献70.