DOCSLIB.ORG

Pyrene-Based Materials for Organic Electronics Teresa M

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Pyrene-Based Materials for Organic Electronics Teresa M REVIEW pubs.acs.org/CR Pyrene-Based Materials for Organic Electronics Teresa M. Figueira-Duarte† and Klaus M€ullen*,‡ †BASF SE, Carl-Bosch-Strasse 38, 67056 Ludwigshafen, Germany ‡Max Planck Institute for Polymer Research, Ackermannweg 10, P.O. Box 3148, Mainz, Germany CONTENTS Greek for “fire”, was attributed since he believed that it was frequently obtained via the reaction of organic substances with 1. Introduction 7260 fire. Later on, in 1871, Gr€abe reported the isolation of pyrene via 2. Electronic and Optoelectronic Organic Devices 7262 extraction with carbon disulfide, which left the accompanying 2.1. Organic Light-Emitting Diodes (OLEDs) 7262 chrysene undissolved.2 Concentration of the solution gave a 2.2. Organic Field-Effect Transistors (OFETs) 7263 crude pyrene, which was further purified via the picrate. Decom- 2.3. Organic Photovoltaic Devices (OPVs) 7263 position of the picrate yielded pyrene as yellow plates. 3. Chemical Modification of Pyrene 7264 Pyrene is also formed in many pyrolytic processes, for example, in the destructive distillation of soft coal tar, by pyrolysis 3.1. 1-Substituted Pyrenes 7264 of acetylene and hydrogen,3 by the zinc-dust distillation of 3.2. 1,3,6,8-Tetrasubstituted Pyrenes 7272 thebenol and thebenin,4 and from petroleum by the catarol 3.3. 1,6- And 1,8-Disubstituted Pyrenes 7274 process.5 Until 1882, an interesting source of pyrene was a special 3.4. 1,3-Disubstituted Pyrenes 7275 distillation of mercury ore as carried out in Idria. The byproduct, 3.5. 2,7-Substituted Pyrenes 7275 which was mixed with mercury, was called “Stupp” and contained 3.6. 4,5,9,10-Substituted Pyrenes 7277 up to 20% pyrene as well as other polycyclic hydrocarbons. The search for an effective method to prepare pyrene lead 4. Pyrenes as Active Components in Devices 7279 Weitzenb€ock in 1913 to the first synthesis of pyrene, starting 6 4.1. 1-Substituted Pyrenes 7279 from o,o0-ditolyl. Until the 1950s, several other preparative 7 16 4.1.1. Linear Structures 7279 routes toward pyrene were presented. À Modernization of 4.1.2. Liquid Crystalline Structures 7290 the distillation process of coal tar, as well as the destructive 4.1.3. Dendritic Structures 7290 hydrogenation of hard coal, yielded considerable quantities of pyrene and other polycyclic hydrocarbons, making pyrene of 4.1.4. Organic Inorganic Hybrids 7293 À commercial use. 4.2. 1,3,6,8-Tetrasubstituted Pyrenes 7293 Pyrene was initially used in the preparation of several deriva- 4.2.1. Linear Structures 7293 tives, such as the pyranthrone, for the synthetic dye industry.17 4.2.2. Liquid Crystalline Structures 7294 Later, in 1954 Forster€ and Kasper reported the first observation 18 4.2.3. Dendritic Structures 7297 of intermolecular excimers in a pyrene solution. This excimer fl 4.3. 1,6- And 1,8-Disubstituted Pyrenes 7299 formation, combined with long-lived excited states, high uor- escence quantum yield,19 exceptional distinction of the fluores- 4.3.1. Linear Structures 7299 cence bands for monomer and excimer, and the sensitivity of its 4.3.2. Liquid Crystalline Structures 7301 excitation spectra to microenvironmental changes,20 brought 4.4. 1,3-Disubstituted Pyrenes 7302 pyrene to the status of a gold standard as a molecular probe of 4.5. 2,7-Disubstituted Pyrenes 7304 microenvironments. Thanks to this attractive combination of 4.6. 4,5,9,10-Substituted Pyrenes 7304 properties, pyrene has become one of the most studied organic 5. Conclusion 7309 molecules in terms of its photophysical properties. The fluorescence properties of pyrene have been utilized over Author Information 7310 the last 50 years in the investigation of water-soluble polymers, Biographies 7310 making pyrene, by far, the most frequently applied dye in References 7310 fluorescence labeled polymers.21,22 The attachment of hydro- phobic pyrene units to water-soluble polymers alters not only the properties of the polymer but also those of the chromophore. The pyrene chromophore is also frequently employed as a probe 1. INTRODUCTION to measure properties of surfactant micelles, phospholipid vesi- Pyrene is the fruit fly of photochemists. Its unique properties cles, and surfactant/polymers aggregates. The tendency of have inspired researchers from many scientific areas, making pyrene and its derivatives to form excimers has been widely pyrene the chromophore of choice in fundamental and applied employed for supramolecular design and for probing the struc- photochemical research. Since the pioneering work of Laurent, tural properties of macromolecular systems. Pyrene labels have who in 1837 discovered pyrene in the residue of the destructive distillation of coal tar,1 this polycyclic aromatic hydrocarbon has Received: December 14, 2010 been the subject of tremendous investigation. The name pyrene, Published: July 11, 2011 r 2011 American Chemical Society 7260 dx.doi.org/10.1021/cr100428a | Chem. Rev. 2011, 111, 7260–7314 Chemical Reviews REVIEW been extensively used in structural studies of proteins and of the optical properties while also influencing the molecular 23 26 27 31 peptides, À but also DNA recognition À and investigation packing. High spatial organization is of great importance for the 32 39 of lipid membranes. À The excimer fluorescence of pyrene construction of devices in order to control the charge carrier and derivatives has been also utilized to sense environmental mobilities. Also the choice of the right processing technique is parameters such as temperature,40 pressure,41 or pH.42 The change crucial for the fabrication of high-performance devices. of the excimer fluorescence intensity reflects changes in the environ- Conjugated organic oligomers and polymers have achieved ment. In addition, it can also be used to detect guest molecules such the status of a major technologically important class of materials. 43 46 47 49 50 57 fi as gases (O2 or NH3), À organic molecules, À metals, À Polymers have the advantages of low cost, ease of modi cation of or other miscellaneous analytes.58 properties by appropriate substitution, and solvent processabil- In addition to excimer sensing, which propelled pyrene to the ity. Oligomers are of particular interest, since they generally status of the most used fluorescent probe, there has been a recent possess good molecular-ordering properties when processed increased interest in the use of pyrene as organic semiconductor using vacuum-sublimation techniques. Since vacuum deposition for application in materials science and organic electronics. Great is often argued to be expensive and limiting toward display size, progress has been made, particularly in the past decade, in the several efforts have been made in order to make oligomers search for organic materials with attractive electronic and photo- soluble in organic solvents with the introduction of proper physical properties for application in a new generation of chemical substituents. Monodisperse conjugated oligomers can 59 61 electronic and optoelectronic devices. À The ability to replace be free from structural defects, possessing high purity from inorganic semiconductors with organic materials will decrease conventional purification methods, allowing a very accurate manufacturing costs and allow fabrication of devices over large relationship between structure and properties. Pyrene-based areas on lightweight and flexible substrates. The appeal of new low-molecular weight organic materials and polymers have been technologies based on organic semiconductors has notably used as active components in molecular electronic devices such promoted the advancement of devices such as organic light- as OLEDs, OFETs, and, more recently, solar cells. emitting diodes (OLEDs), organic photovoltaic cells (OPV), Herein, we provide an overview of the use of pyrene-based organic field-effect transistors (OFETs), organic lasers, and materials in organic electronics illustrating the increased interest memory cells. These devices are being tailored for application of pyrene in electronic devices and highlighting their potential as in flat-panel displays, lighting, RFID (radio frequency identifica- organic semiconductors. In our structure-driven approach, we tion tags), electronic skin, and solar modules. Furthermore, describe many efforts to manage the pyrene chemical challenges flexible organic electronic devices have generated entirely new and, consequently, establish a new pyrene chemistry that allows design concepts for consumer electronics, since they are fully the use of pyrene in organic electronics. Moreover, we also adaptable to complex surface shapes. demonstrate how to control the intermolecular interactions by The key to the conception of high-performance electronic manipulating the complexity of the structure at the molecular organic devices is based on the insight of clear structure level using different substitutions on the pyrene ring. The design property relationships, which can be used to understand the pro-À of different pyrene-based molecular architectures is discussed, as perties of existing devices and predict the ideal material sets for well as the study of the optical and electronic properties plus the utilization in the next generation of electronic devices. Subtle charge transfer processes, which are of particular interest for changes in structure or composition of an organic material can molecular electronics. Furthermore, our study paves the way for greatly alter its bulk properties. In contrast to inorganic semi- the evaluation of these molecular components with respect to conductors, the properties of
Load more

Recommended publications
  • Polycyclic Aromatic Hydrocarbon Structure Index
    NIST Special Publication 922 Polycyclic Aromatic Hydrocarbon Structure Index Lane C. Sander and Stephen A. Wise Chemical Science and Technology Laboratory National Institute of Standards and Technology Gaithersburg, MD 20899-0001 December 1997 revised August 2020 U.S. Department of Commerce William M. Daley, Secretary Technology Administration Gary R. Bachula, Acting Under Secretary for Technology National Institute of Standards and Technology Raymond G. Kammer, Director Polycyclic Aromatic Hydrocarbon Structure Index Lane C. Sander and Stephen A. Wise Chemical Science and Technology Laboratory National Institute of Standards and Technology Gaithersburg, MD 20899 This tabulation is presented as an aid in the identification of the chemical structures of polycyclic aromatic hydrocarbons (PAHs). The Structure Index consists of two parts: (1) a cross index of named PAHs listed in alphabetical order, and (2) chemical structures including ring numbering, name(s), Chemical Abstract Service (CAS) Registry numbers, chemical formulas, molecular weights, and length-to-breadth ratios (L/B) and shape descriptors of PAHs listed in order of increasing molecular weight. Where possible, synonyms (including those employing alternate and/or obsolete naming conventions) have been included. Synonyms used in the Structure Index were compiled from a variety of sources including “Polynuclear Aromatic Hydrocarbons Nomenclature Guide,” by Loening, et al. [1], “Analytical Chemistry of Polycyclic Aromatic Compounds,” by Lee et al. [2], “Calculated Molecular Properties of Polycyclic Aromatic Hydrocarbons,” by Hites and Simonsick [3], “Handbook of Polycyclic Hydrocarbons,” by J. R. Dias [4], “The Ring Index,” by Patterson and Capell [5], “CAS 12th Collective Index,” [6] and “Aldrich Structure Index” [7]. In this publication the IUPAC preferred name is shown in large or bold type.
    [Show full text]
  • On‐Surface Synthesis of Ethynylene‐Bridged Anthracene Polymers
    Angewandte Communications Chemie International Edition:DOI:10.1002/anie.201814154 Surface Chemistry German Edition:DOI:10.1002/ange.201814154 On-Surface Synthesis of Ethynylene-Bridged Anthracene Polymers Ana Sµnchez-Grande,Bruno de la Torre,JosØ Santos,Borja Cirera, Koen Lauwaet, Taras Chutora, Shayan Edalatmanesh, Pingo Mutombo,Johanna Rosen, Radek Zborˇil, Rodolfo Miranda, Jonas Bjçrk,* Pavel Jelínek,* Nazario Martín,* and David Écija* Abstract: Engineering low-band-gap p-conjugated polymers conjugated nanomaterials to be synthesized by wet chemis- is agrowing area in basic and applied research. The main try.[2,3] synthetic challenge lies in the solubility of the starting materials, On-surface synthesis has become apowerful discipline to which precludes advancements in the field. Here,wereport an design many novel molecular compounds,polymers,and on-surface synthesis protocol to overcome such difficulties and nanomaterials with atomistic precision,[4–12] some of them not produce poly(p-anthracene ethynylene) molecular wires on accessible by standard synthetic methods.Additionally,on- Au(111). To this aim, aquinoid anthracene precursor with surface chemistry enables the structural and electronic =CBr2 moieties is deposited and annealed to 400 K, resulting in characterization of the designed products with advanced anthracene-based polymers.High-resolution nc-AFM meas- surface-science techniques.[10,13,14] Recently,and within the urements confirm the nature of the ethynylene-bridge bond scope of on-surface synthesis,particular success
    [Show full text]
  • Chemistry of Acenes, [60]Fullerenes, Cyclacenes and Carbon Nanotubes
    University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 2011 Chemistry of acenes, [60]fullerenes, cyclacenes and carbon nanotubes Chandrani Pramanik University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Pramanik, Chandrani, "Chemistry of acenes, [60]fullerenes, cyclacenes and carbon nanotubes" (2011). Doctoral Dissertations. 574. https://scholars.unh.edu/dissertation/574 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. CHEMISTRY OF ACENES, [60]FULLERENES, CYCLACENES AND CARBON NANOTUBES BY CHANDRANI PRAMANIK B.Sc., Jadavpur University, Kolkata, India, 2002 M.Sc, Indian Institute of Technology Kanpur, India, 2004 DISSERTATION Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Materials Science May 2011 UMI Number: 3467368 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI Dissertation Publishing UMI 3467368 Copyright 2011 by ProQuest LLC. All rights reserved. This edition of the work is protected against unauthorized copying under Title 17, United States Code. ProQuest LLC 789 East Eisenhower Parkway P.O.
    [Show full text]
  • WO 2016/074683 Al 19 May 2016 (19.05.2016) W P O P C T
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2016/074683 Al 19 May 2016 (19.05.2016) W P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C12N 15/10 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/DK20 15/050343 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 11 November 2015 ( 11. 1 1.2015) KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, (25) Filing Language: English PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (26) Publication Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: PA 2014 00655 11 November 2014 ( 11. 1 1.2014) DK (84) Designated States (unless otherwise indicated, for every 62/077,933 11 November 2014 ( 11. 11.2014) US kind of regional protection available): ARIPO (BW, GH, 62/202,3 18 7 August 2015 (07.08.2015) US GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, (71) Applicant: LUNDORF PEDERSEN MATERIALS APS TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, [DK/DK]; Nordvej 16 B, Himmelev, DK-4000 Roskilde DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, (DK).
    [Show full text]
  • Preparative-Scale Synthesis of Nonacene
    1 Preparative-scale synthesis of nonacene Andrej Jančařík1,2*, Jan Holec1, Yuuya Nagata3, Michal Šámal2, Andre Gourdon1* 1) CEMES-CNR, 29 Rue J. Marvig, 31055 Toulouse, France. 2) Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, 16610 Prague 6, Czech Republic. 3) Japan Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, Hokkaido 001-0021, Japan. *emails: [email protected], [email protected] Abstract: During the last years we have witnessed progressive evolution of preparation of acenes with length up to dodecacene by on-surface synthesis in UHV or generation of acenes up to decacene in solid matrices at low temperatures. While these protocols with very specific conditions produce the acenes in amount of few molecules, the strategies leading to the acenes in large quantities dawdle behind. Only recently and after 70 years of synthetic attempts, heptacene has been prepared in bulk phase. However, the preparative scale synthesis of higher homologues still remains a formidable challenge. Here we report the preparation and characterisation of nonacene and show its excellent thermal and in-time stability. Over the last decade, particular attention has been brought to long unsubstituted acenes (longer than pentacene) from both experimental and theoretical points of view.1 The nature of their electronic structure such as gap stabilization2–4 and open shell singlet ground state for longer acenes is still actively discussed.5–9 Furthermore, longer acenes can be seen as the narrowest zig-zag graphene nanoribbons (ZGNR) and could display spin-polarized edge-states of interest for carbon-based spin electronics.10,11 However, acenes longer than pentacene are challenging to prepare and to handle.
    [Show full text]
  • Kuo-Wei Huang
    Kuo-Wei Huang KAUST Catalysis Center and Division of Physical Sciences and Engineering King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia Phone: +966 (0)5 4470 0034; Office: +966 (0)12 808-0328 E-mail: [email protected] EDUCATION: 2000-2004 Ph.D. Stanford University 1993-1997 B.S. National Taiwan University WORK EXPERIENCE: 07.2018-present Professor of Chemical Science, KAUST 07.2014-06.2018 Associate Professor of Chemical Science, KAUST 10.2009-06.2014 Assistant Professor of Chemical Science, KAUST 10.2007-09.2009 Assistant Professor, Department of Chemistry, National University of Singapore 10.2004-09.2007 Goldhaber Distinguished Fellow, Brookhaven National Laboratory 09.1999-07.2000 Full Time Teaching Assistant, Department of Chemistry, National Taiwan University 01.1998-08.1999 Second Lieutenant, Taiwan Military Police Command HONORS, AWARDS, & RECOGNITIONS: 2017 Appreciation of distinguished teaching contribution, Ministry of Education, KSA 2016 Rising Star, International Symposium for Young Chinese Chemists 2016 2015 New Talents: Asia-Pacific, Dalton Transactions 2014 Rising Stars Lectureship, 41st International Conference on Coordination Chemistry 2013-2016 SABIC Presidential Chair Professorship (KAUST) 2013 Asian Rising Stars Lectureship, the 15th Asian Chemical Congress 2012 Danish Chemical Society Lectureship (Denmark) 2012 RIKEN Visiting Fellowship (RIKEN, Japan) 2012 Asian Core Program Lectureship (Singapore) 2011, 2014 Award of Appreciation from King Abdulaziz and his Companions Foundation for Giftedness and Creativity (MAWHIBA) and Ministry of Education, KSA 2010 KAUST 1st and 2nd Seed Fund Program Awards (KAUST) 2008 UK-Singapore Partners In Science Collaboration Development Award 2004-2007 Gertrude and Maurice Goldhaber Distinguished Fellowship (BNL/DOE) 2002-2004 Regina Casper Stanford Graduate Fellowship (Stanford University) 1993-1997 Yuan T.
    [Show full text]
  • Polycyclic Aromatic Hydrocarbons As Model Cases for Structural and Optical Studies R
    Special Issue: Review Commentary Received: 24 August 2009, Revised: 2 October 2009, Accepted: 13 October 2009, Published online in Wiley InterScience: 3 February 2010 (www.interscience.wiley.com) DOI 10.1002/poc.1644 Forever young: polycyclic aromatic hydrocarbons as model cases for structural and optical studies R. Riegera and K. Mu¨ llena* Polycyclic aromatic hydrocarbons (PAHs) are popular research subjects due to their high stability, their rigid planar structure, and their characteristic optical spectra. The recent discovery of graphene, which can be regarded as giant PAH, has further stimulated the interest in this area. For this reason, the relationship between the geometric and electronic structure and the optical spectra of PAHs are reviewed, pointing out the versatile properties of this class of molecules. Extremely stable fully-benzenoid PAHs with high optical gaps are encountered on the one side and the very reactive acenes with low optical gaps on the other side. A huge range of molecular sizes is covered from the simplest case benzene with its six carbon atoms up to disks containing as much as 96 carbon atoms. Furthermore, the impact of non-planarity is discussed as model cases for the highly important fullerenes and carbon nanotubes. The detailed analysis of the electronic structure of PAHs is very important with regard to their application as fluorescent dyes or organic semiconductors. The presented research results shall encourage developments of new PAH structures to exploit novel materials properties. Copyright ß 2010 John Wiley & Sons, Ltd. Keywords: aromaticity; dyes; photophysics; polycyclic aromatic hydrocarbons; UV/vis INTRODUCTION dramatically different optical and chemical properties are observed.
    [Show full text]
  • IJCA 32A(10) 833-836.Pdf
    Indian Journal of Chemistry Vol. 32A, October 1993, pp. 833-836 Approximating the total .7l-electron energy of benzenoid hydrocarbons: Some new estimates of (n,m)-type \I Ivan Gutman* Institute of Chemistry, Academia Sinica, Taipei 11529, Taiwan, ROC and Lemi Turker Department of Chemistry, Middle East Technical University, Ankara, Turkey Received 15 February 1993; accepted 3 May 1993 Three novel lower bounds for the total .7l-electronenergy of benzenoid hydrocarbons have been obtained. These bounds are of (n,m)-type, i.e., they are functions of only the number of carbon at• oms (n) and the number of carbon-carbon bonds (m). Two of them are much better than the previ• ously reported estimates of the same kind. The results obtained shed light on the dependence of the thermodynamic stability of benzenoid hydrocarbons on molecular structure. The extension of the re• sults obtained to non-benzenoid altemant hydrocarbons is straightforward, but requires some cau• tion. The total Jl-electron energy (E), as calculated carbon-carbon bonds. This finding had two signi• within the framework of the tight-binding Huckel ficant consequences. First, it highlighted the im• molecular orbital model, is a quantum-chemical portance of the structural parameters n and m. characteristic of conjugated hydrocarbons (and Second, it shifted the focus of research from find• benzenoid systems in particular) that provides ing approximate formulae for E towards finding useful information about their thermodynamic be• mathematically exact upper and lower estimates haviour. The fundamental problem of how E is for E. related to the (experimentally measurable) heats Since McClelland's seminal paper4, a large of formation and atomization was resolved by number of results in the same field were ob• Schaad and Hess I, who showed that the total en• tained5-1z (see reference 3 for review and further ergy of the a-electrons of the.
    [Show full text]
  • V11 Nonacene.Pdf
    Preparative-scale synthesis of nonacene Andrej Jančařík, Jan Holec, Yuuya Nagata, Michal Šámal, André Gourdon To cite this version: Andrej Jančařík, Jan Holec, Yuuya Nagata, Michal Šámal, André Gourdon. Preparative-scale synthe- sis of nonacene. 2021. hal-03199172 HAL Id: hal-03199172 https://hal.archives-ouvertes.fr/hal-03199172 Preprint submitted on 15 Apr 2021 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. 1 Preparative-scale synthesis of nonacene Andrej Jančařík1,2*, Jan Holec1, Yuuya Nagata3, Michal Šámal2, Andre Gourdon1* 1) CEMES-CNR, 29 Rue J. Marvig, 31055 Toulouse, France. 2) Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, 16610 Prague 6, Czech Republic. 3) Japan Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, Hokkaido 001-0021, Japan. *emails: [email protected], [email protected] Abstract: During the last years we have witnessed progressive evolution of preparation of acenes with length up to dodecacene by on-surface synthesis in UHV or generation of acenes up to decacene in solid matrices at low temperatures. While these protocols with very specific conditions produce the acenes in amount of few molecules, the strategies leading to the acenes in large quantities dawdle behind.
    [Show full text]
  • Excited-State Studies of Polyacenes: a Comparative Picture Using EOMCCSD, CR-EOMCCSD(T), Range-Separated (LR/RT)-TDDFT, TD-PM3, and TD-ZINDO K
    ARTICLE pubs.acs.org/JCTC Excited-State Studies of Polyacenes: A Comparative Picture Using EOMCCSD, CR-EOMCCSD(T), Range-Separated (LR/RT)-TDDFT, TD-PM3, and TD-ZINDO K. Lopata,*,† R. Reslan,‡ M. Kowalska,§ D. Neuhauser,*,‡ N. Govind,*,† and K. Kowalski*,† † William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352, United States ‡ Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, United States § Department of Chemistry, Washington State University Tri-Cities, Richland, Washington 99354, United States À ABSTRACT: The low-lying excited states (La and Lb) of polyacenes from naphthalene to heptacene (N =2 7) are studied using various time-dependent computational approaches. We perform high-level excited-state calculations using equation of motion coupled cluster with singles and doubles (EOMCCSD) and completely renormalized equation of motion coupled cluster with singles, doubles, and perturbative triples (CR-EOMCCSD(T)) and use these results to evaluate the performance of various range-separated exchange- correlation functionals within linear-response (LR) and real-time (RT) time-dependent density functional theories (TDDFT). As has been reported recently, we find that the range-separated family of functionals addresses the well-documented TDDFT failures in describing these low-lying singlet excited states to a large extent and are as about as accurate as results from EOMCCSD on average. Real-time TDDFT visualization shows that the excited state charged densities are consistent with the predictions of the perimeter free electron orbital (PFEO) model. This corresponds to particle-on-a-ring confinement, which leads to the well-known red-shift of the excitations with acene length.
    [Show full text]
  • How Much Aromatic Naphthalene and Graphene Are?
    How much aromatic naphthalene and graphene are? Yashita Y. Singh,a and Vaibhav A. Dixit*b aDepartment of Pharmaceutical Chemistry, School of Pharmacy & Technology Management, Shri Vile Parle Kelavani Mandal’s (SVKM's), Narsee Monjee Institute of Management Studies (NMIMS), Mukesh Patel Technology Park, Babulde, Bank of Tapi River, Mumbai-Agra Road, Shirpur, Dist. Dhule 425405 India. bDepartment of Pharmacy, Birla Institute of Technology and Sciences Pilani (BITS-Pilani), VidyaVihar Campus, street number 41, Pilani, 333031, Rajasthan. India. Phone No. +91 1596 255652, Mob. No. +91-7709129400, Corresponding author: Vaibhav A. Dixit Corresponding author email: [email protected], [email protected] Abstract Naphthalene, (Aromatic stabilization Energy; ASE, 50-60 kcal/mol) polyacenes and graphene are considered aromatic. Existing models for polyacenes predict a linearly increasing ASE and give little insights into their high reactivity and decreasing stability. Graphene’s aromaticity has been studied earlier qualitatively suggesting alternate Clar’s sextet and two-electrons per ring, but ASE estimates have not been reported yet. In this paper, various Heat of Hydrogenation (HoH) and isodesmic schemes have been proposed and compared for the estimation of naphthalene ASE. Results show that HoH schemes are simple to design, are equivalent to isodesmic schemes, and unconjugated unsaturated reference systems predict ASE values in agreement with literature reports. Partially aromatic reference systems underestimate ASE. HoH schemes require calculations for a smaller number of structures, and offer scope for experimental validation, and involve enthalpy differences. Polyacene (X-axis extensions of benzene) ASE estimates (using HoH scheme) correlate well with experimental instability data and offer new physical insights explaining the absence of arbitrarily larger polyacenes.
    [Show full text]
  • Identify Similarities in Diverse Polycyclic Aromatic Hydrocarbons of Asphaltenes and Heavy Oils Revealed by Noncontact Atomic Fo
    Identify Similarities in Diverse Polycyclic Aromatic Hydrocarbons of Asphaltenes and Heavy Oils Revealed by Noncontact Atomic Force Microscopy: Aromaticity, Bonding, and Implications in Reactivity Yunlong Zhang [email protected] Corporate Strategic Research, ExxonMobil Research and Engineering Company, 1545 Route 22 East, Annandale, NJ 08801 Heavy oils are enriched with polycyclic (or polynuclear) aromatic hydrocarbons (PAH or PNA), but characterization of their chemical structures has been a great challenge due to their tremendous diversity. Recently, with the advent of molecular imaging with noncontact Atomic Force Microscopy (nc-AFM), molecular structures of petroleum has been imaged and a diverse range of novel PAH structures was revealed. Understanding these structures will help to understand their chemical reactivities and the mechanisms of their formation or conversion. Studies on aromaticity and bonding provide means to recognize their intrinsic structural patterns which is crucial to reconcile a small number of structures from AFM and to predict infinite number of diverse molecules in bulk. Four types of PAH structures can be categorized according to their relative stability and reactivity, and it was found that the most and least stable types are rarely observed in AFM, with most molecules as intermediate types in a subtle balance of kinetic reactivity and thermodynamic stability. Local aromaticity was found maximized when possible for both alternant and nonalternant PAHs revealed by the aromaticity index NICS (Nucleus-Independent Chemical Shift) values. The unique role of five-membered rings in disrupting the electron distribution was recognized. Especially, the presence of partial double bonds in most petroleum PAHs was identified and their implications in the structure and reactivity of petroleum are discussed.
    [Show full text]