On-Surface Synthesis of Graphene Nanostructures with π
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Azulene Chemistry
Azulene Chemistry What follows is a summary of the synthesis reactions related to Azulene, its generation and its derivatives based on the references I was able to review. I hope that this summary will be of help to those who might be interested in this subject. Nozoe, T., Seto, S., & Matsumura, S. (1962). Synthesis of 2-substituted azulenes by nucleophilic substitution reactions of 2-haloazulene derivatives. Bulletin of the Chemical Society of Japan, 35(12), 1990-1998. Nozoe, T., Takase, K., & Tada, M. (1965). The Anionoid Substitution Reaction of Diethyl 6-Bromoazulene-1, 3- dicarboxylate. Bulletin of the Chemical Society of Japan, 38(2), 247-251. Tada, M. (1966). The Anionoid Substitution Reaction of Diethyl 2-Acetamido-6-bromoazulene-1, 3-dicarboxylate. Bulletin of the Chemical Society of Japan, 39(9), 1954-1961. Saito, M., Morita, T., & Takase, K. (1980). Synthesis of 2-Formylazulene and Its Derivatives by Oxidative Cleavage of 2-Styrylazulenes. Bulletin of the Chemical Society of Japan, 53(12), 3696-3700. Asao, T., & Ito, S. (1996). Synthesis and Properties of Novel Azulenic π-Electronic Compounds. Journal of Synthetic Organic Chemistry, Japan, 54(1), 2-14. Kurotobi, K., Tabata, H., Miyauchi, M., Mustafizur, R. A., Migita, K., Murafuji, T., ... & Fujimori, K. (2003). The first generation of azulenyl-lithium and-magnesium: A novel, versatile method of introducing a substituent at the 2- position of an azulene skeleton. Synthesis, 1(01), 0030-0034. Crombie, A. L., Kane, J. L., Shea, K. M., & Danheiser, R. L. (2004). Ring expansion-annulation strategy for the synthesis of substituted azulenes and oligoazulenes. 2. Synthesis of azulenyl halides, sulfonates, and azulenylmetal compounds and their application in transition-metal-mediated coupling reactions. -
Annual Progress Report of the Condensed Matter Physics and Chemistry Department 1 January - 31 December 1998
Ris0-R-1O99(EN) DK9900089 Annual Progress Report of the Condensed Matter Physics and Chemistry Department 1 January - 31 December 1998 Edited by K. Bechgaard, K.N. Clausen, R. Feidenhans'l and I. Johannsen Ris0 National Laboratory, Roskilde, Denmark April 1999 30-31 Ris0-R-1O99(EN) Annual Progress Report of the Condensed Matter Physics and Chemistry Department 1 January - 31 December 1998 Edited by K. Bechgaard, K.N. Clausen, R. Feidenhans'l and I. Johannsen Ris0 National Laboratory, Roskilde, Denmark April 1999 Abstract The Condensed Matter Physics and Chemistry Department is concerned with both fundamental and applied research into the physical and chemical properties of materials. The principal activities in the year 1998 are presented in this progress report. The research in physics is concentrated on neutron and x-ray scattering measurements and the problems studied include two- and three-dimensional structures, magnetic ordering and spin dynamics, superconductivity, phase transitions and nano-scale structures. The research in chemistry includes chemical synthesis and physico-chemical investigation of small molecules and polymers, with emphasis on polymers with new optical properties, block copolymers, surface-modified polymers, and supramolecular structures. Theoretical work related to these problems is undertaken, including Monte Carlo simulations, computer simulation of molecules and polymers and methods of data analysis. The readers are invited to contact the department or the authors of the individual contributions for more detailed information than can be given in this report. The postal address is: Condensed Matter Physics and Chemistry Department, Ris0 National Laboratory. P.O. Box 49, DK-4000 Roskilde, Denmark. E-mail addresses may be found on the last page of this report. -
Π‐Extended Diaza[7]Helicenes by Hybridization of Naphthalene
Full Paper Chemistry—A European Journal doi.org/10.1002/chem.202003402 & Organic chemistry |HotPaper| p-Extended Diaza[7]helicenes by Hybridization of Naphthalene Diimides and Hexa-peri-hexabenzocoronenes Carolin Dusold,[a] Dmitry I. Sharapa,[b] Frank Hampel,[a] and Andreas Hirsch*[a] Abstract: The synthesis of an unprecedented, p-extended mation of the diaza[7]helicene moiety in the final Scholl oxi- hexabenzocorene (HBC)-based diaza[7]helicene is presented. dation is favoured, affording the symmetric p-extended heli- The target compound was synthesized by an ortho-fusion of cene as the major product as apair of enantiomers. The sep- two naphthalene diimide (NDI) units to aHBC-skeleton. A aration of the enantiomers was successfully accomplished combination of Diels–Alder and Scholl-type oxidation reac- by HPLC involving achiral stationary phase. The absolute tions involving asymmetric di-NDI-tolane precursor were configuration of the enantiomers was assigned by compari- crucial for the very selectiveformation of the helical super- son of circular dichroismspectrawith quantum mechanical structure via ahexaphenyl-benzene (HPB) derivative. The for- calculations. Introduction can notably tune optical, electronical and supramolecular properties.[10] Elongation of the spiral arrangementofthe con- The development of nonplanar PAHs is currently an emerging jugated p-systemrepresents the most common way to pre- field in synthetic organic chemistry.[1] Among the most impor- pare higher helicene derivatives.[11] In contrasttothat, the ex- tant -
Anti‐Aromatic Versus Induced Paratropicity ... -.:. Michael Pittelkow
Angewandte Forschungsartikel Chemie Deutsche Ausgabe:DOI:10.1002/ange.201913552 Circulenes Internationale Ausgabe:DOI:10.1002/anie.201913552 Anti-Aromatic versus Induced Paratropicity:Synthesis and InterrogationofaDihydro-diazatrioxa[9]circulene with aProton Placed Directly above the Central Ring Stephan K. Pedersen, Kristina Eriksen, Nataliya N. Karaush-Karmazin, Boris Minaev, Hans gren, Gleb V. Baryshnikov* und Michael Pittelkow* Abstract: We present ahigh-yielding intramolecular oxidative coupling within adiazadioxa[10]helicene to give adihydro- diazatrioxa[9]circulene.This is the first [n]circulene contain- ing more than eight ortho-annulated rings (n > 8). The single- crystal X-raystructure reveals atight columnar packing, with aproton from apendant naphthalene moiety centred directly abovethe central nine-membered ring. This distinct environ- ment induces asignificant magnetic deshielding effect on that particular proton as determined by 1HNMR spectroscopy. The origin of the deshielding effect was investigated computation- ally in terms of the NICS values.Itisestablished that the deshielding effect originates from an induced paratropic ring current from the seven aromatic rings of the [9]circulene structure,and is not due to the nine-membered ring being antiaromatic.UV/Vis spectroscopyreveals more efficient Figure 1. Simplified illustration of the influence of diatropic and para- conjugation in the prepared diazatrioxa[9]circulene compared tropic ring currents on the 1Hchemical shift inside and outside of to the parent helical azaoxa[10]helicenes,and -
[7]Helicene to a Planar Hetero[8]Circulene Bodil Lousen,[A] Stephan K
Communication Chemistry—A European Journal doi.org/10.1002/chem.201905339 & Non-Planar Aromatics Compressing aNon-Planar Aromatic Heterocyclic [7]Helicene to a Planar Hetero[8]Circulene Bodil Lousen,[a] Stephan K. Pedersen,[a] Pernille Bols,[a] Kasper H. Hansen,[a] MichelleR.Pedersen,[a] Ole Hammerich,[a] Sergey Bondarchuk,[b] Boris Minaev,[b] Glib V. Baryshnikov,[c] Hans gren,[c, d] and MichaelPittelkow*[a] cally chiral moleculeshave found vast applications in such di- Abstract: This work describes asyntheticapproachwhere verse fields as molecular recognition,catalysis anddetection or anon-planar aromatic heterocyclic [7]helicene is com- emissionofcircularlypolarized light.[2–5] Structurally related pressedtoyield ahetero[8]circulene containing an inner motifstothe [n]helicenes are the [n]circulenes. These struc- antiaromatic cyclooctatetraene (COT) core. This [8]circu- tures also consist of ortho-annulatedaromatic rings, but in- lene consists of four benzene rings and four heterocyclic stead forms acyclic structure, having acentral ring with n rings, and it is the first heterocyclic[8]circulenecontaining sides.Itisillustrative to view the all-benzene series of [n]circu- three differentheteroatoms. The synthetic pathway pro- lenes,which consistsofthe bowl-shaped carba[5]circulene ceeds via athe flattened dehydro-hetero[7]helicene, (corannulene), the planar carba[6]circulene(coronene) andthe which is partially ahelicene and partially acirculene:itis saddle-shaped[7]- and [8]circulenes. Hetero[8]circulenes incor- non-planar and helically chiral as helicenes, and contains a poratingfour five-membered heterocycles(furans,pyrroles, COT motif like [8]circulenes. The antiaromaticity of the thiophenes)are planar,[6,7] and these structures can be viewed COT core is confirmed by nucleusindependent chemical as containingantiaromaticcyclooctatetraene(COT) cores. -
Synthesis of a [5] Helicene-Based Chiral Polymer
Research Article Academ J Polym Sci Volume 2 Issue 5 - May 2019 Copyright © All rights are reserved by Thieo Hogen Esch E DOI: 10.19080/AJOP.2019.02.555598 Synthesis of A [5] Helicene-Based Chiral Polymer Janet Olsen M and Thieo Hogen Esch E* Department of Chemistry, University of Southern California, Loker Hydrocarbon Research Institute, USA Submission: March 18, 2019; Published: May 21, 2019 *Corresponding author: Thieo Hogen Esch E, Department of Chemistry, University of Southern California, Loker Hydrocarbon Research Institute, Los Angeles, CA90089-1661, USA Abstract reaction between this helicene derivative and p-diiodo benzene gave polymer 11, which is soluble in many common organic solvents. Peaks in A copolymer precursor, an alkoxy-functionalized 3,12-diethyenyl [5] helicene, was prepared in seven consecutive steps. A Pd (0)-catalyzed the UV spectrum of 11 are shifted to the red when compared with the spectrum of monomeric analogue 12, presumably because of extended conjugationKeywords: between the helicene comonomers and the aryl connector units. 3,12-diethyenyl [5] helicene; P-Diiodo Benzene; Organic Light-Emitting Diodes; Benzylidene; Helicene Polymer Precursors; Methyl Ether; Polymeric Helicenes; Naphthyl Groups Introduction merization with a benzylidine or similar arylidene connector Helicenes are polycyclic structures composed of n or- group should allow increased delocalization. However, helicenes tho-fused aromatic rings, where n refers to the number of rings. with polymerization potential represent a more synthetically repulsion between the terminal rings, causing the molecule to When n reaches five or more, the molecule experiences steric more effective helicene polymer precursors is of interest. - challenging target [11,14,15]. -
Synthesis of Azahelicenes Through Mallory Reaction of Imine Precursors: Corannulene Substrates Provide an Exception to the Rule
Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Synthesis of azahelicenes through Mallory reaction of imine precursors: corannulene substrates Cite this: Chem. Sci.,2021,12,3977 All publication charges for this article provide an exception to the rule in oxidative have been paid for by the Royal Society † of Chemistry photocyclizations of diarylethenes a b a a Animesh Ghosh, Daniel´ Csok´ as,´ Maja Budanovic,´ Richard D. Webster, b a Imre Papai´ and Mihaiela C. Stuparu * Typically, the synthesis of phenanthrene-based polycyclic aromatic hydrocarbons relies on the Mallory reaction. In this approach, stilbene (PhCH]CHPh)-based precursors undergo an oxidative photocyclization reaction to join the two adjacent aromatic rings into an extended aromatic structure. Received 9th December 2020 However, if one C]C carbon atom is replaced by a nitrogen atom (C]N), the synthesis becomes Accepted 22nd January 2021 practically infeasible. Here, we show the very first examples of a successful Mallory reaction on stilbene- DOI: 10.1039/d0sc06730j like imine precursors involving the molecularly curved corannulene nucleus. The isolated yields exceed Creative Commons Attribution-NonCommercial 3.0 Unported Licence. rsc.li/chemical-science 90% and the resulting single and double aza[4]helicenes exhibit adjustable high affinity for electrons. Introduction eliminates possible side-reactions of typically electron rich aromatics with oxygen. Therefore, high yields can be obtained. Diarylethenes/stilbenes are known to undergo a trans-to-cis -
Twofold Π‑Extension of Polyarenes Via Double and Triple Radical Alkyne Peri-Annulations
pubs.acs.org/JACS Article Twofold π‑Extension of Polyarenes via Double and Triple Radical Alkyne peri-Annulations: Radical Cascades Converging on the Same Aromatic Core Edgar Gonzalez-Rodriguez, Miguel A. Abdo, Gabriel dos Passos Gomes, Suliman Ayad, Frankie D. White, Nikolay P. Tsvetkov, Kenneth Hanson, and Igor V. Alabugin* Cite This: J. Am. Chem. Soc. 2020, 142, 8352−8366 Read Online ACCESS Metrics & More Article Recommendations *sı Supporting Information ABSTRACT: A versatile synthetic route to distannyl-substituted polyarenes was developed via double radical peri-annulations. The cyclization precursors were equipped with propargylic OMe traceless directing groups (TDGs) for regioselective Sn-radical attack at the triple bonds. The two peri-annulations converge at a variety of polycyclic cores to yield expanded difunctionalized polycyclic aromatic hydrocarbons (PAHs). This approach can be extended to triple peri-annulations, where annulations are coupled with a radical cascade that connects two preexisting aromatic cores − via a formal C H activation step. The installed Bu3Sn groups serve as chemical handles for further functionalization via direct cross- coupling, iodination, or protodestannylation and increase solubility of the products in organic solvents. Photophysical studies reveal fl fl that the Bu3Sn-substituted PAHs are moderately uorescent, and their protodestannylation results in an up to 10-fold uorescence quantum yield enhancement. DFT calculations identified the most likely possible mechanism of this complex chemical transformation involving two independent peri-cyclizations at the central core. ■ INTRODUCTION the synthesis of fused helicenes and “defect-free” polycyclic 49−52 Nanographenes (NGs), large polycyclic aromatic hydro- aromatics in a modular and scalable way. In these carbons (PAHs), and graphene nanoribbons (GNRs) have transformations, the TDG serves two critical roles. -
Title Facile Synthesis of Fluorescent Hetero[8]Circulene Analogues With
Facile synthesis of fluorescent hetero[8]circulene analogues Title with tunable solubilities and optical properties Matsuo, Yusuke; Chen, Fengkun; Kise, Koki; Tanaka, Author(s) Takayuki; Osuka, Atsuhiro Citation Chemical Science (2019), 10(48): 11006-11012 Issue Date 2019-12-28 URL http://hdl.handle.net/2433/255894 This article is licensed under a Creative Commons Attribution- Right NonCommercial 3.0 Unported Licence. Type Journal Article Textversion publisher Kyoto University Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Facile synthesis of fluorescent hetero[8]circulene analogues with tunable solubilities and optical Cite this: Chem. Sci.,2019,10, 11006 † All publication charges for this article properties have been paid for by the Royal Society of Chemistry Yusuke Matsuo, Fengkun Chen, Koki Kise, Takayuki Tanaka * and Atsuhiro Osuka Hetero[8]circulenes are an interesting class of polycyclic heteroaromatic molecules having rigid and planar structures, which are promising in light of their potential applications for OLEDs, OFETs and so forth. Although their synthetic methods have been developed in some specific cases, a facile synthetic protocol of novel hetero[8]circulenes with tunable properties is highly desirable. We herein report the unexpected formation of methoxy-substituted quasi-aza[8]circulene and its conversion into unprecedented triazaoxa[8]circulene. The structures and optical properties were comparatively studied. Remarkably, triazaoxa[8]circulene is highly soluble in THF, acetone and DMSO mainly because of effective hydrogen-bonding of the NH moieties to these solvents. Their highly soluble nature in various Creative Commons Attribution-NonCommercial 3.0 Unported Licence. solvents enabled us to study the solvent effects of these molecules. -
Adsorption Geometry Determination of Single Molecules by Atomic Force Microscopy
Adsorption geometry determination of single molecules by atomic force microscopy 1, 2 2 1 Bruno Schuler, ⇤ Wei Liu, Alexandre Tkatchenko, Nikolaj Moll, Gerhard Meyer,1 Anish Mistry,3 David Fox,3 and Leo Gross1 1IBM Research – Zurich, S¨aumerstrasse 4, 8803 R¨uschlikon,Switzerland 2Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany 3University of Warwick, Gibbet Hill, CV34 Warwick, UK (Dated: July 24, 2013) We measured the adsorption geometry of single molecules with intra-molecular resolution using noncontact atomic force microscopy (NC-AFM) with functionalized tips. The lateral adsorption position was determined with atomic resolution, adsorption height di↵erences with a precision of 3pm, andtiltsofthemolecularplanewithin0.2 ◦.Themethodwasappliedtofive⇡-conjugated molecules, including three molecules from the olympicene family, adsorbed on Cu(111). For the olympicenes, we found that the substitution of a single atom leads to strong variations of the adsorption height, as predicted by state-of-the-art density-functional theory including van der Waals interactions with collective substrate response e↵ects (DFT+vdWsurf). PACS numbers: 68.37.Ps, 34.20.Gj, 68.35.-p, 68.43.-h In noncontact atomic force microscopy (NC-AFM) the benzo[cd]pyrene (olympicene), benzo[cd]pyrene (radical), crucial factors a↵ecting the image contrast are the chem- 6H-benzo[cd]pyren-6-one (ketone), which di↵er in their ical interaction between probe and sample [1], the tip chemical structure only by one atom. Finally, adsorption termination [2–4] and the adsorbate geometry [5]. For sites of the olympicenes are determined by atomically re- organic molecules on metal substrates, the adsorption ge- solving the substrate and the adsorbed molecule in one ometry (adsorption site, height, tilt) is intimately linked image. -
Extension to Nanographenes with Zig-Zag Edges
ARTICLE DOI: 10.1038/s41467-018-07095-z OPEN Dehydrative π-extension to nanographenes with zig-zag edges Dominik Lungerich 1,2, Olena Papaianina1, Mikhail Feofanov 1, Jia Liu3, Mirunalini Devarajulu3, Sergey I. Troyanov4, Sabine Maier 3 & Konstantin Amsharov 1 Zig-zag nanographenes are promising candidates for the applications in organic electronics due to the electronic properties induced by their periphery. However, the synthetic access to 1234567890():,; these compounds remains virtually unexplored. There is a lack in efficient and mild strategies origins in the reduced stability, increased reactivity, and low solubility of these compounds. Herein we report a facile access to pristine zig-zag nanographenes, utilizing an acid-promoted intramolecular reductive cyclization of arylaldehydes, and demonstrate a three-step route to nanographenes constituted of angularly fused tetracenes or pentacenes. The mild conditions are scalable to gram quantities and give insoluble nanostructures in close to quantitative yields. The strategy allows the synthesis of elusive low bandgap nanographenes, with values as low as 1.62 eV. Compared to their linear homologues, the structures have an increased stability in the solid-state, even though computational analyses show distinct diradical character. The structures were confirmed by X–ray diffraction or scanning tunneling microscopy. 1 Department of Chemistry and Pharmacy, Organic Chemistry II, Friedrich-Alexander-University Erlangen-Nuernberg, Nikolaus-Fiebiger-Str. 10, 91058 Erlangen, Germany. 2 Department of Chemistry & Molecular Technology Innovation Presidential Endowed Chair, University of Tokyo, 7-3-1 Hongo, Bunkyo- ku, Tokyo 113-0033, Japan. 3 Department of Physics, Friedrich-Alexander-University Erlangen-Nuernberg, Erwin-Rommel-Str. 1, 91058 Erlangen, Germany. 4 Chemistry Department, Moscow State University, Leninskie Gory, Moscow, Russia 119991. -
Olympicenes on the Cu(111) Surface
Letter pubs.acs.org/JPCL Identical Binding Energies and Work Functions for Distinct Adsorption Structures: Olympicenes on the Cu(111) Surface † ‡ § ∥ ⊥ ¶ § § § Wei Liu, , Bruno Schuler, Yong Xu, , , Nikolaj Moll, Gerhard Meyer, Leo Gross, † ∇ and Alexandre Tkatchenko*, , † Nano Structural Materials Center, School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, Jiangsu, China ‡ Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany § IBM Research, Zurich, 8803 Rüschlikon, Switzerland ∥ State Key Laboratory of Low Dimensional Quantum Physics, Department of Physics, Tsinghua University, Beijing 100084, China ⊥ Collaborative Innovation Center of Quantum Matter, Beijing 100084, China ¶ RIKEN Center for Emergent Matter Science (CEMS), Wako, Saitama 351-0198, Japan ∇ Physics and Materials Science Research Unit, University of Luxembourg, L-1511, Luxembourg *S Supporting Information ABSTRACT: Reliability is one of the major concerns and challenges in designing organic/ inorganic interfaces for (opto)electronic applications. Even small structural differences for molecules on substrates can result in a significant variation in the interface functionality, due to the strong correlation between geometry, stability, and electronic structure. Here, we employed state-of-the-art first-principles calculations with van der Waals interactions, in combination with atomic force microscopy experiments, to explore the interaction mechanism for three structurally related olympicene