Impact of Molecular Orientation and Packing Density on Electronic Polarization in the Bulk and at Surfaces of Organic Semiconductors

KAUST Repository

Ryno, Sean; Risko, Chad; Bredas, Jean-Luc

2016-01-01

The polarizable environment surrounding charge carriers in organic semiconductors impacts the efficiency of the charge transport process. Here, we consider two representative organic semiconductors, tetracene and rubrene, and evaluate

Mechanism of Singlet Fission in Thin Films of 1,3-Diphenylisobenzofuran

Czech Academy of Sciences Publication Activity Database

Schrauben, J. N.; Ryerson, J. L.; Michl, Josef; Johnson, J. C.

2014-01-01

Roč. 136, č. 20 (2014), s. 7363-7373 ISSN 0002-7863 Institutional support: RVO:61388963 Keywords : excimer forming crystal * exciton fission * tetracene Subject RIV: CC - Organic Chemistry Impact factor: 12.113, year: 2014

Charge transfer between acenes and PbS nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Dissanayake, D M N M [Solid State Electronics Laboratory, University of Michigan, Ann Arbor, MI 48109-2122 (United States); Hatton, R A [Department of Chemistry, University of Warwick, Coventry CV4 7AL (United Kingdom); Lutz, T [Departments of Chemistry and Physics, Imperial College, London SW7 2AY (United Kingdom); Curry, R J; Silva, S R P [Advanced Technology Institute, University of Surrey, Guildford GU2 7XH (United Kingdom)], E-mail: ndissa@umich.edu

2009-05-13

Organic-inorganic hybrid heterojunctions have potential as the basis for future photovoltaic devices. Herein, we report the results of investigations exploring the possibility of using pentacene and tetracene as photoelectron donors in conjunction with PbS nanocrystals (PbS-NCs). Photoinduced charge transfer was probed using external quantum efficiency measurements on acene:PbS-NC hybrid photovoltaic devices in conjunction with photoluminescence studies of the corresponding bilayer films. It is shown that photoelectron transfer from pentacene to the PbS-NCs is inefficient as compared to that between tetracene and PbS-NCs. The latter case can be rationalized in terms of the energy level alignment at the heterojunction assuming a common vacuum level. However, in the case of pentacene:PbS-NC junctions an interfacial energy level shift must be considered in order to explain the observations.

BAJOPAS_18 - 31_Gidado1

African Journals Online (AJOL)

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angles were found to be so closed to 1200 at both levels of theory for all basis sets used suggesting .... including Tetracene, in the universe (Hoover, 2014). ... is the self-consistent field energy, f is the electric field, a is a nuclear coordinate,.

Strong CH/O interactions between polycyclic aromatic hydrocarbons and water: Influence of aromatic system size.

Science.gov (United States)

Veljković, Dušan Ž

2018-03-01

Energies of CH/O interactions between water molecule and polycyclic aromatic hydrocarbons with a different number of aromatic rings were calculated using ab initio calculations at MP2/cc-PVTZ level. Results show that an additional aromatic ring in structure of polycyclic aromatic hydrocarbons significantly strengthens CH/O interactions. Calculated interaction energies in optimized structures of the most stable tetracene/water complex is -2.27 kcal/mol, anthracene/water is -2.13 kcal/mol and naphthalene/water is -1.97 kcal/mol. These interactions are stronger than CH/O contacts in benzene/water complex (-1.44 kcal/mol) while CH/O contacts in tetracene/water complex are even stronger than CH/O contacts in pyridine/water complexes (-2.21 kcal/mol). Electrostatic potential maps for different polycyclic aromatic hydrocarbons were calculated and used to explain trends in the energies of interactions. Copyright © 2017 Elsevier Inc. All rights reserved.

Singlet Fission in Rubrene Derivatives: Impact of Molecular Packing

KAUST Repository

Sutton, Christopher

2017-03-13

We examine the properties of six recently synthesized rubrene derivatives (with substitutions on the side phenyl rings) that show vastly different crystal structures. In order to understand how packing in the solid state affects the excited states and couplings relevant for singlet fission, the lowest excited singlet (S), triplet (T), multiexciton (TT), and charge-transfer (CT) states of the rubrene derivatives are compared to known singlet fission materials [tetracene, pentacene, 5,12-diphenyltetracene (DPT), and rubrene itself]. While a small difference of less than 0.2 eV is calculated for the S and TT energies, a range of 0.50 to 1.2 eV in the CT energies and nearly 3 orders of magnitude in the electronic couplings are computed for the rubrene derivatives in their crystalline packings, which strongly affects the role of the CT state in facilitating SF. To rationalize experimental observations of singlet fission occurring in amorphous phases of rubrene, DPT, and tetracene, we use molecular dynamics (MD) simulations to assess the impact of molecular packing and orientations and to gain a better understanding of the parameters that control singlet fission in amorphous films compared to crystalline packings. The MD simulations point to a crystalline-like packing for thin films of tetracene; on the other hand, DPT, rubrene, and the rubrene derivatives all show various degrees of disorder with a number of sites that have larger electronic couplings than in the crystal, which can facilitate singlet fission in such thin films. Our analysis underlines the potential of these materials as promising candidates for singlet fission and helps understand how various structural motifs affect the critical parameters that control the ability of a system to undergo singlet fission.

Pseudomorphic growth of organic semiconductor thin films driven by incommensurate epitaxy

International Nuclear Information System (INIS)

Sassella, A.; Campione, M.; Raimondo, L.; Borghesi, A.; Bussetti, G.; Cirilli, S.; Violante, A.; Goletti, C.; Chiaradia, P.

2009-01-01

A stable pseudomorphic phase of α-quaterthiophene, a well known organic semiconductor, is obtained by growing films with organic molecular beam epitaxy (OMBE) on a single crystal of another organic semiconductor, namely, tetracene. The structural characteristics of the new phase are investigated by monitoring in situ the OMBE process by reflectance anisotropy spectroscopy; thus assessing that incommensurate epitaxy is in this case, the driving force for tuning the molecular packing in organic molecular films and in turn, their solid state properties

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations. 3; The Polyacenes Anthracene, Tetracence, and Pentacene

Science.gov (United States)

Hudgins, D. M.; Allamandola, L. J.

1995-01-01

Gaseous, ionized polycyclic aromatic hydrocarbons (PAHS) are thought to be responsible for a very common family of interstellar infrared emission bands. Unfortunately, very little infrared spectroscopic data are available on ionized PAHS. Here we present the near- and mid-infrared spectra of the polyacene cations anthracene, tetracene, and pentacene. We also report the vibrational frequencies and relative intensities of the pentacene anion. The cation bands corresponding to the CC modes are typically about 10-20 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 3-20 times weaker than in the neutral species. This behavior is similar to that found for most other PAH cations. The most intense PAH cation bands fall within the envelopes of the most intense interstellar features. The strongest absorptions in the polyacenes anthracene, tetracene, and pentacene tend to group around 1400/cm (between about 1340 and 1500/cm) and near 1180/cm, regions of only moderate interstellar emission. These very strong polyacene bands tend to fall in gaps in the spectra of the other PAH cations studied to date suggesting that while PAHs with polyacene structures may contribute to specific regions of the interstellar emission spectra, they are not dominant members of the interstellar PAH family.

Carrier-doped aromatic hydrocarbons: a new platform in condensed matter chemistry and physics.

Science.gov (United States)

Heguri, Satoshi; Tanigaki, Katsumi

2018-02-27

High-quality bulk samples of the first four polyacenes, which are naphthalene, anthracene, tetracene, and pentacene, doped with alkali metal in 1 : 1 and 1 : 2 stoichiometries were prepared and their fundamental properties were systematically studied. A new systematic understanding on the electronic states of electron-doped polyacenes sensitive to the energetic balance among on-site Coulomb repulsion, bandwidth and the Peierls instability was provided. The carrier-doped typical aromatic hydrocarbons showed a large variety of properties as well as charge transfer complexes and metal-doped fullerides. We open a new avenue for organometallic and inorganic chemistry.

Comment on: Negative ions, molecular electron affinity and orbital structure of cata-condensed polycyclic aromatic hydrocarbons by Rustem V. Khatymov, Mars V. Muftakhov and Pavel V. Shchukin.

Science.gov (United States)

Chen, Edward S; Chen, Edward C M

2018-02-15

The anion mass spectral lifetimes for several aromatic hydrocarbons reported in the subject article were related to significantly different electron affinities. The different values are rationalized using negative ion mass spectral data. Electron affinities for polycyclic aromatic hydrocarbons are reported from the temperature dependence of unpublished electron capture detector data. These are compared with published values and the largest values are assigned to the ground state. The ground state adiabatic electron affinities: (eV) pentacene, 1.41 (3); tetracene, 1.058 (5); benz(a)pyrene, 0.82 (4); benz(a) anthracene, 0.69 (2) anthracene, 0.68 (2); and pyrene, 0.59 (1) are used to assign excited state adiabatic electron affinities: (eV) tetracene: 0.88 (4); anthracene 0.53 (1); pyrene, 0.41 (1); benz(a)anthracene, 0.39 (10); chrysene, 0.32 (1); and phenanthrene, 0.12 (2) and ground state adiabatic electron affinities: (eV) dibenz(a,j)anthracene, 0.69 (3); dibenz(a,h)anthracene, 0.68 (3); benz(e)pyrene, 0.60 (3); and picene, 0.59 (3) from experimental data. The lifetime of benz(a)pyrene is predicted to be larger than 150 μs and for benzo(c)phenanthrene and picene about 40 μs, from ground state adiabatic electron affinities. The assignments of adiabatic electron affinities of aromatic hydrocarbons determined from electron capture detector and mass spectrometric data to ground and excited states are supported by constant electronegativities. A set of consistent ground state adiabatic electron affinities for 15 polycyclic aromatic hydrocarbons is related to lifetimes from the subject article. Copyright © 2017 John Wiley & Sons, Ltd.

Optical spectra obtained from amorphous films of rubrene: Evidence for predominance of twisted isomer

Science.gov (United States)

Kytka, M.; Gisslen, L.; Gerlach, A.; Heinemeyer, U.; Kováč, J.; Scholz, R.; Schreiber, F.

2009-06-01

In order to investigate the optical properties of rubrene we study the vibronic progression of the first absorption band (lowest π →π∗ transition). We analyze the dielectric function ɛ2 of rubrene in solution and thin films using the displaced harmonic oscillator model and derive all relevant parameters of the vibronic progression. The findings are supplemented by density functional calculations using B3LYP hybrid functionals. Our theoretical results for the molecule in two different conformations, i.e., with a twisted or planar tetracene backbone, are in very good agreement with the experimental data obtained for rubrene in solution and thin films. Moreover, a simulation based on the monomer spectrum and the calculated transition energies of the two conformations indicates that the thin film spectrum of rubrene is dominated by the twisted isomer.

Linear-dendritic supramolecular complexes as nanoscale reaction vessels for "green" chemistry. Diels-Alder reactions between fullerene C60 and polycyclic aromatic hydrocarbons in aqueous medium.

Science.gov (United States)

Simonyan, Arsen; Gitsov, Ivan

2008-10-21

This study describes the first Diels-Alder (DA) reaction performed in aqueous medium with highly hydrophobic compounds-fullerene (C 60) as the dienophile and anthracene (An) or tetracene (Tet) as the dienes, respectively. The reactions are performed in nanocontainers, constructed by self-assembly of linear-dendritic amphiphilic copolymers with poly(ethylene glycol), PEG or poly(ethylene oxide), PEO as the hydrophilic blocks and poly(benzyl ether) monodendrons as the hydrophobic fragments: G3PEO13k, dG3 and dG2. Comparative studies under identical conditions are carried out with an amphiphilic linear-linear copolymer, poly(styrene)1800- block-PEO2100, PSt-PEO, and the nonionic surfactant Igepal CO-720, IP720. The binding affinity of supermolecules built of these amphiphiles toward the DA reagents decreases in the following order: G3PEO13k > dG3 > PSt-PEO > dG2 > IP720. The kinetic constant of binding is evaluated for tetracene and decreases in a similar fashion: 5 x 10 (-7) M/min (G3PEO13k), through 4 x 10 (-7) M/min (PSt-PEO) down to 1.5 x 10 (-7) M/min for IP720. The mobility of substrates encapsulated in the micellar core, estimated by pyrene fluorescence decay, is 95-121 ns for the micelles of the linear-dendritic copolymers and notably higher for PSt-PEO (152 ns), revealing the much denser interior of the linear analogue. The apparent kinetic constant for the DA reaction of C 60 and Tet within the G3PEO13k supermolecule in aqueous medium is markedly higher than in organic solvent (toluene), 208 vs 1.82 M /min. With G3PEO13k the conversions reach 49% for the DA reaction between C 60 and An, and 55% for C 60 and Tet. Besides the monoadduct (26.5% yield) the reaction with An produces exclusively increasing amounts of D 2 h -symmetric antipodal bis-adduct, whose yield reaches up to 22.5% after 48 h. In addition to the environmentally friendly conditions notable advantages of the synthetic strategy described are the extended stability of the linear

Electronic relaxation processes in polyatomic molecules. Progress report, October 1, 1975--September 30, 1976

International Nuclear Information System (INIS)

Lim, E.C.

1976-09-01

Excitation energy dependence of radiationless decay rate under collision-free conditions was utilized as a probe of intramolecular vibrational relaxation in tetracene and pentacene. The results give evidence of vibrational relaxation which competes with electronic relaxation. The substitution dependence of T 1 (nπ*) → S 0 radiationless transition in monocyclic diazines and the temperature dependence of S 1 non-radiative decay rate in alcoholic solutions of polycyclic monoazines indicate that the vibronic interaction between the lowest energy nπ* and ππ* states leads to a rapid radiationless deactivation of the lower of the two electronic states. Finally, a photon-counting spectrofluorometer of very high sensitivity was constructed, and it was used to record T 2 → T 1 fluorescence in bromoanthracenes and S 2 → S 1 fluorescence in azulene. These spectra represent the first bona-fide, or the most convincing, observation of fluorescence between excited electronic states

What is new in the world of superconductors?

International Nuclear Information System (INIS)

Das, M.P.

2002-01-01

Full text: Ever since its discovery in 1911 by Heike Kamerlingh-Onnes in Leiden, superconductivity has promised tantalising possibilities of widespread applications. After 1986 its occurrence in cuprates above the liquid nitrogen temperature reaffirmed its capabilities for very many practical uses. More recently a number of novel materials namely intercalated fullerenes (C-60) and n-cenes (anthra-cene, tetra-cene and penta-cenes), a simple bimetallic alloy (MgB2), and ferromagnetic materials under high pressure including Fe, ZrZn2, and UGe2 have surprised us with their peculiar superconducting properties. In this talk I shall give a pedagogic survey of some of our current understanding- how these novel materials superconduct. I shall highlight a host of observable anomalies associated with these superconductors and discuss if their occurrence throws any light on the microscopic understanding of the superconducting phenomenon. I shall illustrate with a number of practical applications accomplished to date

Rubrene endoperoxide acetone monosolvate

Directory of Open Access Journals (Sweden)

Kiyoaki Shinashi

2012-04-01

Full Text Available The title acetone solvate, C42H28O2·C3H6O [systematic name: 1,3,10,12-tetraphenyl-19,20-dioxapentacyclo[10.6.2.02,11.04,9.013,18]icosa-2(11,3,5,7,9,13,15,17-octaene acetone monosolvate], is a photooxygenation product of rubrene (systematic name: 5,6,11,12-tetraphenyltetracene. The molecule bends at the bridgehead atoms, which are linked by the O—O transannular bond, with a dihedral angle of 49.21 (6° between the benzene ring and the naphthalene ring system of the tetracene unit. In the crystal, the rubrene molecules are linked by C—H...O hydrogen bonds into a column along the c axis. The acetone solvent molecules form a dimer around a crystallographic inversion centre through a carbonyl–carbonyl dipolar interaction. A C—H...O hydrogen bond between the rubrene and acetone molecules is also observed.

Dynamics of Singlet Fission and Electron Injection in Self-Assembled Acene Monolayers on Titanium Dioxide

Energy Technology Data Exchange (ETDEWEB)

Johnson, Justin C [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Pace, Natalie A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Arias, Dylan H [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Christensen, Steven T [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Granger, Devin B. [University of Kentucky; Anthony, John E. [University of Kentucky

2018-02-26

We employ a combination of linear spectroscopy, electrochemistry, and transient absorption spectroscopy to characterize the interplay between electron transfer and singlet fission dynamics in polyacene-based dyes attached to nanostructured TiO2. For triisopropyl silylethynyl (TIPS)-pentacene, we find that the singlet fission time constant increases to 6.5 ps on a nanostructured TiO2 surface relative to a thin film time constant of 150 fs, and that triplets do not dissociate after they are formed. In contrast, TIPS-tetracene singlets quickly dissociate in 2 ps at the molecule/TiO2 interface, and this dissociation outcompetes the relatively slow singlet fission process. The addition of an alumina layer slows down electron injection, allowing the formation of triplets from singlet fission in 40 ps. However, the triplets do not inject electrons, which is likely due to a lack of sufficient driving force for triplet dissociation. These results point to the critical balance required between efficient singlet fission and appropriate energetics for interfacial charge transfer.

Interfacial electronic structure of Na deposited on rubrene thin film studied by synchrotron radiation photoemission

International Nuclear Information System (INIS)

Wei, Ching-Hsuan; Cheng, Chiu-Ping; Lin, Hong-Cheu; Pi, Tun-Wen

2015-01-01

Graphical abstract: - Highlights: • Na deposited on rubrene had undergone three-stage development process via (1) atomic diffusion, (2) atomic incorporation in the surface region, (3) formation of a metallic film. • High resolution core-level photoemission was used to determine the location of the doped Na atoms, which is affiliated at the end position of the tetracene-like backbone. • Na metal was formed on the rubrene thin film. • Ionization potential of the organic molecule regulated with different Na doping concentration could be controllable and favorable in practical applications. - Abstract: The electronic structure of rubrene doped with various concentrations of Na was studied by synchrotron-radiation photoemission. Three stages of development were found with increasing Na concentration; Na penetrating deep into the organic film, followed by development of gap states, and ended with a metallic Na film. The charge transfer from Na to rubrene resulted in a vacuum-level shift. By doping Na into rubrene, we could control the IP of the organic molecule, which is favorable for application in organic semiconductor devices.

Synthesis of extended polycyclic aromatic hydrocarbons by oxidative tandem spirocyclization and 1,2-aryl migration

Science.gov (United States)

Zhang, Xuan; Xu, Zhanqiang; Si, Weili; Oniwa, Kazuaki; Bao, Ming; Yamamoto, Yoshinori; Jin, Tienan

2017-04-01

The extended polycyclic aromatic hydrocarbons (PAHs) have received significant interdisciplinary attention due to their semiconducting applications in diverse organic electronics as well as intriguing structural interests of well-defined graphene segments. Herein, a highly efficient oxidative spirocyclization and 1,2-aryl migration tandem synthetic method for the construction of extended polyaromatic hydrocarbons (PAHs) has been developed. The CuCl-catalyst/PhCO3 tBu or DDQ oxidation system in the presence of trifluoroacetic acid enables the selective single-electron oxidation to take place preferentially at the more electron-rich alkene moiety of o-biphenylyl-substituted methylenefluorenes, giving rise to the subsequent tandem process. A variety of structurally diverse extended PAHs including functionalized dibenzo[g,p]chrysenes, benzo[f]naphtho[1,2-s]picene, hexabenzo[a,c,fg,j,l,op]tetracene, tetrabenzo[a,c,f,m]phenanthro[9,10-k]tetraphene, tetrabenzo[a,c,f,k]phenanthro[9,10-m]tetraphene, tetrabenzo[a,c,f,o]phenanthro[9,10-m]picene and S-type helicene have been readily synthesized.

Probing the (110)-Oriented plane of rutile ZnF2: A DFT investigation

Science.gov (United States)

Tamijani, Ali Abbaspour; Ebrahimiaqda, Elham

2017-12-01

For many years, rutile-like crystals have given rise to pronounced enthusiasm amongst mineralogists. In this context, rutile-type ZnF2 has found numerous applications across a variety of disciplines, ranging from material sciences to optoelectronics. Surprisingly, very limited literature is concerned with the molecular adsorption on ZnF2 surfaces and related energetics. Additionally, surface probing with small particles is a well-entrenched technique to analyze the interfacial properties. In this regard, small organic species are valuable picks. In the present work, we have employed electronic structure calculations to simulate the adsorption of methane, chloroform, pyrrole, benzene, naphthalene, anthracene, tetracene and pentacene at the (110) plane of rutile ZnF2. Dispersion-corrected DFT method was chosen to predict the binding energies and structures of molecule-adsorbed surfaces. Interestingly, a linear proportionality relationship was found between the binding energies of aromatic adsorbates and their respective molecular lengths. By applying this relationship, we were able to predict the adsorption energy of pentacene on ZnF2 to within 2% of our DFT-based result.

The nature of singlet excitons in oligoacene molecular crystals

KAUST Repository

Yamagata, H.; Norton, J.; Hontz, E.; Olivier, Y.; Beljonne, D.; Brédas, J. L.; Silbey, R. J.; Spano, F. C.

2011-01-01

A theory for polarized absorption in crystalline oligoacenes is presented, which includes Frenkel exciton coupling, the coupling between Frenkel and charge-transfer (CT) excitons, and the coupling of all neutral and ionic excited states to the dominant ring-breathing vibrational mode. For tetracene, spectra calculated using all Frenkel couplings among the five lowest energy molecular singlet states predict a Davydov splitting (DS) of the lowest energy (0-0) vibronic band of only -32cm-1, far smaller than the measured value of 631cm-1 and of the wrong sign-a negative sign indicating that the polarizations of the lower and upper Davydov components are reversed from experiment. Inclusion of Frenkel-CT coupling dramatically improves the agreement with experiment, yielding a 0-0 DS of 601cm-1 and a nearly quantitative reproduction of the relative spectral intensities of the 0-n vibronic components. Our analysis also shows that CT mixing increases with the size of the oligoacenes. We discuss the implications of these results on exciton dissociation and transport. © 2011 American Institute of Physics.

Optical band gaps of organic semiconductor materials

Science.gov (United States)

Costa, José C. S.; Taveira, Ricardo J. S.; Lima, Carlos F. R. A. C.; Mendes, Adélio; Santos, Luís M. N. B. F.

2016-08-01

UV-Vis can be used as an easy and forthright technique to accurately estimate the band gap energy of organic π-conjugated materials, widely used as thin films/composites in organic and hybrid electronic devices such as OLEDs, OPVs and OFETs. The electronic and optical properties, including HOMO-LUMO energy gaps of π-conjugated systems were evaluated by UV-Vis spectroscopy in CHCl3 solution for a large number of relevant π-conjugated systems: tris-8-hydroxyquinolinatos (Alq3, Gaq3, Inq3, Al(qNO2)3, Al(qCl)3, Al(qBr)3, In(qNO2)3, In(qCl)3 and In(qBr)3); triphenylamine derivatives (DDP, p-TTP, TPB, TPD, TDAB, m-MTDAB, NPB, α-NPD); oligoacenes (naphthalene, anthracene, tetracene and rubrene); oligothiophenes (α-2T, β-2T, α-3T, β-3T, α-4T and α-5T). Additionally, some electronic properties were also explored by quantum chemical calculations. The experimental UV-Vis data are in accordance with the DFT predictions and indicate that the band gap energies of the OSCs dissolved in CHCl3 solution are consistent with the values presented for thin films.

HIGH-RESOLUTION IR ABSORPTION SPECTROSCOPY OF POLYCYCLIC AROMATIC HYDROCARBONS: THE REALM OF ANHARMONICITY

Energy Technology Data Exchange (ETDEWEB)

Maltseva, Elena; Buma, Wybren Jan [University of Amsterdam, Science Park 904, 1098 XH Amsterdam (Netherlands); Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Tielens, Alexander G. G. M. [Leiden Observatory, Niels Bohrweg 2, 2333 CA Leiden (Netherlands); Huang, Xinchuan; Lee, Timothy J. [SETI Institute, 189 Bernardo Avenue, Suite 100, Mountain View, CA 94043 (United States); Oomens, Jos, E-mail: w.j.buma@uva.nl, E-mail: petrignani@strw.leidenuniv.nl [Radboud University, Toernooiveld 7, 6525 ED Nijmegen (Netherlands)

2015-11-20

We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3-μm CH stretching region of polycyclic aromatic hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold (∼4 K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions with a Fermi-resonance treatment that utilizes intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main bands that fall within 0.5% of the experimental frequencies. The implications for the aromatic infrared bands, specifically the 3-μm band, are discussed.

Dioxin analysis by gas chromatography-Fourier transform ion cyclotron resonance mass spectrometry (GC-FTICRMS).

Science.gov (United States)

Taguchi, Vince Y; Nieckarz, Robert J; Clement, Ray E; Krolik, Stefan; Williams, Robert

2010-11-01

The feasibility of utilizing a gas chromatograph-tandem quadrupole-Fourier transform ion cyclotron resonance mass spectrometer (GC-MS/MS-FTICRMS) to analyze chlorinated-dioxins/furans (CDDs/CDFs) and mixed halogenated dioxins/furans (HDDs/HDFs) was investigated by operating the system in the GC-FTICRMS mode. CDDs/CDFs and mixed HDDs/HDFs could be analyzed at 50,000 to 100,000 resolving power (RP) on the capillary gas chromatographic time scale. Initial experiments demonstrated that 1 pg of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and 5 pg of 2-bromo-3,7,8-trichlorodibenzo-p-dioxin (BTrCDD) could be detected. The feasibility of utilizing an FTICRMS for screening of CDDs/CDFs, HDDs/HDFs and related compounds was also investigated by analyzing an extract from vegetation exposed to fall-out from an industrial fire. CDDs/CDFs, chlorinated pyrenes and chlorinated tetracenes could be detected from a Kendrick plot analysis of the ultrahigh resolution mass spectra. Mass accuracies were of the order of 0.5 ppm on standards with external mass calibration and 1 ppm on a sample with internal mass calibration. Copyright © 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

Predictive modeling of nanoscale domain morphology in solution-processed organic thin films

Science.gov (United States)

Schaaf, Cyrus; Jenkins, Michael; Morehouse, Robell; Stanfield, Dane; McDowall, Stephen; Johnson, Brad L.; Patrick, David L.

2017-09-01

The electronic and optoelectronic properties of molecular semiconductor thin films are directly linked to their extrinsic nanoscale structural characteristics such as domain size and spatial distributions. In films prepared by common solution-phase deposition techniques such as spin casting and solvent-based printing, morphology is governed by a complex interrelated set of thermodynamic and kinetic factors that classical models fail to adequately capture, leaving them unable to provide much insight, let alone predictive design guidance for tailoring films with specific nanostructural characteristics. Here we introduce a comprehensive treatment of solution-based film formation enabling quantitative prediction of domain formation rates, coverage, and spacing statistics based on a small number of experimentally measureable parameters. The model combines a mean-field rate equation treatment of monomer aggregation kinetics with classical nucleation theory and a supersaturation-dependent critical nucleus size to solve for the quasi-two-dimensional temporally and spatially varying monomer concentration, nucleation rate, and other properties. Excellent agreement is observed with measured nucleation densities and interdomain radial distribution functions in polycrystalline tetracene films. Numerical solutions lead to a set of general design rules enabling predictive morphological control in solution-processed molecular crystalline films.

High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons: The Realm of Anharmonicity

Science.gov (United States)

Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2016-01-01

We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3 micrometers CH stretching region of Polycyclic Aromatic Hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold ((is) approximately 4K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions enhanced with a Fermi-resonance treatment that utilizes intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main modes that fall within 0.5% of the experimental frequencies. The implications for the Aromatic Infrared Bands, specifically the 3-m band are discussed.

Investigating the effect of acene-fusion and trifluoroacetyl substitution on the electronic and charge transport properties by density functional theory

Directory of Open Access Journals (Sweden)

Ahmad Irfan

2016-05-01

Full Text Available We designed novel derivatives of 4,6-di(thiophen-2-ylpyrimidine (DTP. Two benchmark strategies including mesomerically deactivating group, as well as the extension of π-conjugation bridge (acene-fusion have been employed to enhance the electrical and charge transport properties. The density functional theory (DFT and time dependent DFT methods have been used to get optimized geometries in ground and first excited state, respectively. The structural properties (geometric parameters, electronic properties (frontier molecular orbitals; highest occupied and lowest unoccupied molecular orbitals, photophysical properties (absorption, fluorescence and phosphorescence, and important charge transport properties are discussed to establish a molecular level structure–property relationship among these derivatives. Our calculated electronic spectra i.e., absorption, fluorescence and phosphorescence have been found in good semi-quantitative agreement with available experimental data. All the newly designed derivatives displayed significantly improved electron injection ability than those of the parent molecule. The values of reorganization energy and transfer integral elucidate that DTP is a potential hole transport material. Based on our present investigation, it is expected that the naphtho and anthra derivatives of DTP are better hole transporters than those of some well-known charge transporter materials like naphthalene, anthracene, tetracene and pentacene.

Electro-optical and charge injection investigations of the donor-π-acceptor triphenylamine, oligocene–thiophene–pyrimidine and cyanoacetic acid based multifunctional dyes

Directory of Open Access Journals (Sweden)

Ahmad Irfan

2015-10-01

Full Text Available The corner stone of present study is to tune the electro-optical and charge transport properties of donor-bridge-acceptor (D-π-A triphenylamine (TPA derivatives. In the present investigation, an electron deficient moiety (pyrimidine, electron-rich moiety (thiophene and oligocene (benzene, naphthalene, anthracene, tetracene and pentacene have been incorporated as π-spacer between the donor TPA unit and cyanoacetic acid acceptor and anchoring group. The elongation of bridge usually affects the energy levels, i.e., higher the highest occupied molecular orbital (HOMO while lower the lowest unoccupied molecular orbital (LUMO thus reduces the HOMO–LUMO energy gap. The lowered LUMO energy levels of cyano-{2-[6-(4-diphenylamino-phenyl-pyrimidin-4-yl]-tetraceno[2,3-b]thiophen-8-yl}-acetic acid (TPA-PTT4 and cyano-{2-[6-(4-diphenylamino-phenyl-pyrimidin-4-yl]-pentaceno[2,3-b]thiophen-9-yl}-acetic acid (TPA-PPT5 dyes revealed that electron injected from dye to semiconductor surface might be auxiliary stable resulting in impediment of quenching. The broken co-planarity between the π-spacer conceiving LUMO and the TPA moiety would help to impede the recombination process. Moreover, it is expected that TPA derivatives with the tetracenothiophene and pentacenothiophene moieties as π-bridge would show better photovoltaic performance due to lowered LUMO energy level, higher electronic coupling constant, light harvesting efficiency and electron injection values.

Acenes, Heteroacenes and Analogous Molecules for Organic Photovoltaic and Field Effect Transistor Applications

Science.gov (United States)

Granger, Devin Benjamin

Polycyclic aromatic hydrocarbons composed of benzenoid rings fused in a linear fashion comprise the class of compounds known as acenes. The structures containing three to six ring fusions are brightly colored and possess band gaps and charge transport efficiencies sufficient for semiconductor applications. These molecules have been investigated throughout the past several decades to assess their optoelectronic properties. The absorption, emission and charge transport properties of this series of molecules has been studied extensively to elucidate structure-property relationships. A wide variety of analogous molecules, incorporating heterocycles in place of benzenoid rings, demonstrate similar properties to the parent compounds and have likewise been investigated. Functionalization of acene compounds by placement of groups around the molecule affects the way in which molecules interact in the solid state, in addition to the energetics of the molecule. The use of electron donating or electron withdrawing groups affects the frontier molecular orbitals and thus affects the optical and electronic gaps of the molecules. The use of bulky side groups such as alkylsilylethynyl groups allows for crystal engineering of molecular aggregates, and changing the volume and dimensions of the alkylsilyl groups affects the intermolecular interactions and thus changes the packing motif. In chapter 2, a series of tetracene and pentacene molecules with strongly electron withdrawing groups is described. The investigation focuses on the change in energetics of the frontier molecular orbitals between the base acene and the nitrile and dicyanovinyl derivatives as well as the differences between the pentacene and tetracene molecules. The differences in close packing motifs through use of bulky alkylsilylethynyl groups is also discussed in relation to electron acceptor material design and bulk heterojunction organic photovoltaic characteristics. Chapter 3 focuses on molecular acceptor and

Quantitative analysis of intermolecular interactions in orthorhombic rubrene

Directory of Open Access Journals (Sweden)

Venkatesha R. Hathwar

2015-09-01

Full Text Available Rubrene is one of the most studied organic semiconductors to date due to its high charge carrier mobility which makes it a potentially applicable compound in modern electronic devices. Previous electronic device characterizations and first principles theoretical calculations assigned the semiconducting properties of rubrene to the presence of a large overlap of the extended π-conjugated core between molecules. We present here the electron density distribution in rubrene at 20 K and at 100 K obtained using a combination of high-resolution X-ray and neutron diffraction data. The topology of the electron density and energies of intermolecular interactions are studied quantitatively. Specifically, the presence of Cπ...Cπ interactions between neighbouring tetracene backbones of the rubrene molecules is experimentally confirmed from a topological analysis of the electron density, Non-Covalent Interaction (NCI analysis and the calculated interaction energy of molecular dimers. A significant contribution to the lattice energy of the crystal is provided by H—H interactions. The electron density features of H—H bonding, and the interaction energy of molecular dimers connected by H—H interaction clearly demonstrate an importance of these weak interactions in the stabilization of the crystal structure. The quantitative nature of the intermolecular interactions is virtually unchanged between 20 K and 100 K suggesting that any changes in carrier transport at these low temperatures would have a different origin. The obtained experimental results are further supported by theoretical calculations.

Mechanisms of interaction of radiation with matter

International Nuclear Information System (INIS)

Geacintov, N.E.; Pope, M.

1993-01-01

This project is concerned with the mechanisms by which polynuclear aromatic (PNA) compounds on the one hand, and ionizing radiation on the other, cause damage to DNA. PNA compounds constitute an important class of environmental pollutants derived from energy-related sources which, upon metabolic activation to diolepoxide derivatives, produce bulky PNA-DNA lesions interfere with the normal DNA replication and transcription processes, and give rise to mutations and the initiation of tumors. Chiral and other stereochemical effects play a key role in determining the biological effects of a given PNA diol epoxide and the potentially mutagenic lesions which are formed. New and efficient methods for synthesizing stereochemically pure and precisely positioned PNA diol epoxide-DNA lesions in small DNA fragments are reported here. We have elucidated the structures of three stereoisomeric benzo[a]pyrene diol epoxide-DNA adducts. How these adducts affect on DNA polymerase fidelity, transcription, and DNA repair are currently being investigated with respect to detailed structure-biological activity correlations. Spectroscopic techniques such as circular dichroism, fluorescence, and photoionization play an important role in the characterizations of the PNA adducts. A new method was developed for measuring the lifetimes as well as the energies of picosecond duration electronically excited states. Using this technique, it is proposed that short-lived (15 ps) charge-transfer (CT) states in the PNA compound tetracene are activated by a 20 ps laser pulse; an unusual external photoemission echo do to the recombination of CT states is observed 85 ps after the pulse

Far infrared (terahertz) spectroscopy of a series of polycyclic aromatic hydrocarbons and application to structure interpretation of asphaltenes and related compounds.

Science.gov (United States)

Cataldo, Franco; Angelini, Giancarlo; García-Hernández, D Aníbal; Manchado, Arturo

2013-07-01

A series of 33 different polycyclic aromatic hydrocarbons (PAHs) were studied by far infrared spectroscopy (terahertz spectroscopy) in the spectral range comprised between 600 and 50 cm(-1). In addition to common PAHs like naphthalene, anthracene, phenanthrene, fluoranthene, picene, pyrene, benzo[α]pyrene, and perylene, also quite unusual PAHs were studied like tetracene, pentacene, acenaphtene, acenaphtylene, triphenylene, and decacyclene. A series of alkylated naphthalenes and anthracenes were studied as well as methypyrene. Partially or totally hydrogenated PAHs were also object of the present investigation, ranging from tetrahydronaphthalene (tetralin) to decahydronaphthalene (decalin), 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, hexahydropyrene, and dodecahydrotriphenylene. Finally, the large and quite rare PAHs coronene, quaterrylene, hexabenzocoronene, and dicoronylene were studied by far infrared spectroscopy. The resulting reference spectra were used in the interpretation of the chemical structure of asphaltenes (as extracted from a heavy petroleum fraction and from bitumen), the chemical structures of other petroleum fractions known as DAE (distillate aromatic extract) and RAE (residual aromatic extract), and a possible interpretation of components of the chemical structure of anthracite coal. Asphaltenes, heavy petroleum fractions, and coal were proposed as model compounds for the interpretation of the emission spectra of certain proto-planetary nebulae (PPNe) with a good matching in the mid infrared between the band pattern of the PPNe emission spectra and the spectra of these oil fractions or coal. Although this study was finalized in an astrochemical context, it may find application also in the petroleum and coal chemistry. Copyright © 2013 Elsevier B.V. All rights reserved.

Green primary explosives: 5-nitrotetrazolato-N2-ferrate hierarchies.

Science.gov (United States)

Huynh, My Hang V; Coburn, Michael D; Meyer, Thomas J; Wetzler, Modi

2006-07-05

The sensitive explosives used in initiating devices like primers and detonators are called primary explosives. Successful detonations of secondary explosives are accomplished by suitable sources of initiation energy that is transmitted directly from the primaries or through secondary explosive boosters. Reliable initiating mechanisms are available in numerous forms of primers and detonators depending upon the nature of the secondary explosives. The technology of initiation devices used for military and civilian purposes continues to expand owing to variations in initiating method, chemical composition, quantity, sensitivity, explosive performance, and other necessary built-in mechanisms. Although the most widely used primaries contain toxic lead azide and lead styphnate, mixtures of thermally unstable primaries, like diazodinitrophenol and tetracene, or poisonous agents, like antimony sulfide and barium nitrate, are also used. Novel environmentally friendly primary explosives are expanded here to include cat[Fe(II)(NT)(3)(H(2)O)(3)], cat(2)[Fe(II)(NT)(4)(H(2)O)(2)], cat(3)[Fe(II)(NT)(5)(H(2)O)], and cat(4)[Fe(II)(NT)(6)] with cat = cation and NT(-) = 5-nitrotetrazolato-N(2). With available alkaline, alkaline earth, and organic cations as partners, four series of 5-nitrotetrazolato-N(2)-ferrate hierarchies have been prepared that provide a plethora of green primaries with diverse initiating sensitivity and explosive performance. They hold great promise for replacing not only toxic lead primaries but also thermally unstable primaries and poisonous agents. Strategies are also described for the systematic preparation of coordination complex green primaries based on appropriate selection of ligands, metals, and synthetic procedures. These strategies allow for maximum versatility in initiating sensitivity and explosive performance while retaining properties required for green primaries.

Probing the accuracy and precision of Hirshfeld atom refinement with HARt interfaced with Olex2.

Science.gov (United States)

Fugel, Malte; Jayatilaka, Dylan; Hupf, Emanuel; Overgaard, Jacob; Hathwar, Venkatesha R; Macchi, Piero; Turner, Michael J; Howard, Judith A K; Dolomanov, Oleg V; Puschmann, Horst; Iversen, Bo B; Bürgi, Hans-Beat; Grabowsky, Simon

2018-01-01

Hirshfeld atom refinement (HAR) is a novel X-ray structure refinement technique that employs aspherical atomic scattering factors obtained from stockholder partitioning of a theoretically determined tailor-made static electron density. HAR overcomes many of the known limitations of independent atom modelling (IAM), such as too short element-hydrogen distances, r ( X -H), or too large atomic displacement parameters (ADPs). This study probes the accuracy and precision of anisotropic hydrogen and non-hydrogen ADPs and of r ( X -H) values obtained from HAR. These quantities are compared and found to agree with those obtained from (i) accurate neutron diffraction data measured at the same temperatures as the X-ray data and (ii) multipole modelling (MM), an established alternative method for interpreting X-ray diffraction data with the help of aspherical atomic scattering factors. Results are presented for three chemically different systems: the aromatic hydro-carbon rubrene (orthorhombic 5,6,11,12-tetra-phenyl-tetracene), a co-crystal of zwitterionic betaine, imidazolium cations and picrate anions (BIPa), and the salt potassium hydrogen oxalate (KHOx). The non-hydrogen HAR-ADPs are as accurate and precise as the MM-ADPs. Both show excellent agreement with the neutron-based values and are superior to IAM-ADPs. The anisotropic hydrogen HAR-ADPs show a somewhat larger deviation from neutron-based values than the hydrogen SHADE-ADPs used in MM. Element-hydrogen bond lengths from HAR are in excellent agreement with those obtained from neutron diffraction experiments, although they are somewhat less precise. The residual density contour maps after HAR show fewer features than those after MM. Calculating the static electron density with the def2-TZVP basis set instead of the simpler def2-SVP one does not improve the refinement results significantly. All HARs were performed within the recently introduced HARt option implemented in the Olex2 program. They are easily launched

Interaction of radiation with matter

International Nuclear Information System (INIS)

1978-05-01

During 1978, these conclusions were reached and are reported: Innershell Coulomb ionization cross sections show significant relativistic effects even for the lighter atoms, because ionization occurs near the nucleus in our range of low particle energies. Atomic excitation and ionization in deep atom--atom collisions can be described in terms of a model with random walk in energy space to the continuum. This model may be best suited for the analysis of heavy ion--atom encounters. Energy straggling of charged particles in matter are affected by inhomogeneities in and surface conditions of the medium. Using molecular ions as incident projectiles it is concluded that moving protons do not have bound states in solids. Projectiles in close proximity to each other exhibit larger energy losses than isolated projectiles indicating interactions of the electron density fluctuations established behind moving projectiles in solids. Heterogeneous oxidation of SO 2 by holes has been found at an organic (PAH) aqueous interface. The process has a reasonably high quantum efficiency (approx. >0.1) for anthracene. Various experiments are being carried out to determine whether SO 3 /sup =/ or HSO 3 - is involved. Photoemission from PAH organic aerosols has been investigated. The rate of emission from tetracene is found to go as the maximum electron kinetic energy cubed. It is found that the particle may be used as an electron spectrometer for determining the electron kinetic energy distribution. A new way of characterizing small aerosols by mass has been found. The method utilizes the detection of a single electron imbalance in a Millikan chamber. Aerosol masses as small as 1 pgm can be measured to better than 1%. The potent carcinogen benzo (a) pyrene (BP) when metabolized in vivo is found to have a physical structure in which the BP7,8-dihydrodial 9,10-oxide adduct (BPDE) is bound on the outside of the helix. Models and measurements support this conclusion

Photophysical characterization and time-resolved spectroscopy of a anthradithiophene dimer: exploring the role of conformation in singlet fission

KAUST Repository

Dean, Jacob C.

2017-08-18

Quantitative singlet fission has been observed for a variety of acene derivatives such as tetracene and pentacene, and efforts to extend the library of singlet fission compounds is of current interest. Preliminary calculations suggest anthradithiophenes exhibit significant exothermicity between the first optically-allowed singlet state, S1, and 2 × T1 with an energy difference of >5000 cm−1. Given the fulfillment of this ingredient for singlet fission, here we investigate the singlet fission capability of a difluorinated anthradithiophene dimer (2ADT) covalently linked by a (dimethylsilyl)ethane bridge and derivatized by triisobutylsilylethynyl (TIBS) groups. Photophysical characterization of 2ADT and the single functionalized ADT monomer were carried out in toluene and acetone solution via absorption and fluorescence spectroscopy, and their photo-initiated dynamics were investigated with time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopy. In accordance with computational predictions, two conformers of 2ADT were observed via fluorescence spectroscopy and were assigned to structures with the ADT cores trans or cis to one another about the covalent bridge. The two conformers exhibited markedly different excited state deactivation mechanisms, with the minor trans population being representative of the ADT monomer showing primarily radiative decay, while the dominant cis population underwent relaxation into an excimer geometry before internally converting to the ground state. The excimer formation kinetics were found to be solvent dependent, yielding time constants of ∼1.75 ns in toluene, and ∼600 ps in acetone. While the difference in rates elicits a role for the solvent in stabilizing the excimer structure, the rate is still decidedly long compared to most singlet fission rates of analogous dimers, suggesting that the excimer is neither a kinetic nor a thermodynamic trap, yet singlet fission was still not observed. The result

CCDC 980734: Experimental Crystal Structure Determination : 9,18-bis(4-t-butylphenyl)-5,14-bis((4-t-butylphenyl)ethynyl)dinaphtho[3,2,1-de:3',2',1'-mn]tetracene chloroform solvate

KAUST Repository

Sun, Zhe; Zheng, Bin; Hu, Pan; Huang, Kuo-Wei; Wu, Jishan

2014-01-01

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An In Silico Study on the Isomers of Pentacene: The Case for Air-Stable and Alternative C22H14 Acenes for Organic Electronics.

Science.gov (United States)

Jones, Leighton; Lin, Long

2017-04-13

Pentacene is one of the most investigated candidates for organic thin film transistor (OTFT) applications over the last few decades even though it unstable in air (E g = 1.80 eV), owing in part to its planar nature and high charge-transfer mobilities as both a single crystal (35 cm 2 V -1 s -1 ) and as a thin-film (3.0 cm 2 V -1 s -1 ). Until now, picene is the only isomer of pentacene to be investigated for organic electronic applications, due to its greater stability (E g = 4.21 eV) and high-charge transfer mobility (3.0 cm 2 V -1 s -1 ); even benefiting from oxygen doping. In the present study, a total of 12 fused-ring isomers (including pentacene, picene and ten other structures) of the formula C 22 H 14 were analyzed and investigated for their electronic and optical properties for worth in OTFT applications. We screened several pure and hybrid DFT functionals against the experimental frontier molecular orbitals (FMOs) of pentacene, then deployed Marcus Theory, Koopmans' Theorem and Green's function with the P3 electron propagator variant, for the internal hole reorganization energy, the hole transfer integral (via the "splitting-in-dimer method" at d = 3.0, 3.5, and 4.0 Å), the charge transfer rate constant, and vertical ionization energies. Using these as a basis, we studied pentacene's isomers and found that the four nonplanar structures, namely, benzo[g]chrysene (3), naphtho[c]phenanthrene (7), benzo[c]chrysene (11) and dibenzo[c,c']phenthrene (12), are (I) more stable than pentacene, by up to 2 eV, and (II) have relatively similar ionization energies (7.5-7.6 eV) to those of picene's experimental value (7.51 eV). The largest charge transfer rates at 3.5 Å dimer separations were given by the isomers benzo[b]chrysene 4, naphtha[c]phenanthrene 7, dibenzo[a,c]anthracene 8 and benzo[a]tetracene 10 and found to be 2.92, 1.72, 1.30, and 3.09 × 10 14 s -1 respectively. In comparison to that of pentacene (K CT = 3.97 × 10 14 s -1 ), these unusual isomers are

The Larger Linear N-Heteroacenes

KAUST Repository

Bunz, Uwe H. F.

2015-01-01

tetraazaacenes, azapentacenes, azahexacenes, and azaheptacenes are accessible. Pd-catalysis-based coupling methods for both activated and nonactivated o-dihalides have been developed. The larger azaacene representatives were unknown before but are of conceptual and theoretical interest. Azaacenes, particularly the symmetrical bis(triisopropylsilylethynyl)-substituted tetraazapentacene, are primarily used in organic field-effect transistors, but smaller azaacenes shine in the field as organic light-emitting diode (OLED) emitters. Diazatetracenes and substituted benzoquinoxalines are successful, improving electron injection and increasing OLED brightness, as compared to that of pure tetracenes. On the basis of the acene framework, nitrogen atoms in the acene perimeter and aggregation-precluding molecular appendages create solid-state fluorescent species. Azaacenes are expanding the range and complementing the purview of acenes in organic electronic applications. They enlarge the profiles of acenes with respect to synthetic strategies, structures, properties, and applications.

The Larger Linear N-Heteroacenes

KAUST Repository

Bunz, Uwe H. F.

2015-06-16

tetraazaacenes, azapentacenes, azahexacenes, and azaheptacenes are accessible. Pd-catalysis-based coupling methods for both activated and nonactivated o-dihalides have been developed. The larger azaacene representatives were unknown before but are of conceptual and theoretical interest. Azaacenes, particularly the symmetrical bis(triisopropylsilylethynyl)-substituted tetraazapentacene, are primarily used in organic field-effect transistors, but smaller azaacenes shine in the field as organic light-emitting diode (OLED) emitters. Diazatetracenes and substituted benzoquinoxalines are successful, improving electron injection and increasing OLED brightness, as compared to that of pure tetracenes. On the basis of the acene framework, nitrogen atoms in the acene perimeter and aggregation-precluding molecular appendages create solid-state fluorescent species. Azaacenes are expanding the range and complementing the purview of acenes in organic electronic applications. They enlarge the profiles of acenes with respect to synthetic strategies, structures, properties, and applications.

Unconventional, Chemically Stable, and Soluble Two-Dimensional Angular Polycyclic Aromatic Hydrocarbons: From Molecular Design to Device Applications

KAUST Repository

Zhang, Lei

2015-03-17

Polycyclic aromatic hydrocarbons (PAHs), consisting of laterally fused benzene rings, are among the most widely studied small-molecule organic semiconductors, with potential applications in organic field-effect transistors (OFETs) and organic photovoltaics (OPVs). Linear acenes, including tetracene, pentacene, and their derivatives, have received particular attention due to the synthetic flexibility in tuning their chemical structure and properties and to their high device performance. Unfortunately, longer acenes, which could exhibit even better performance, are susceptible to oxidation, photodegradation, and, in solar cells which contain fullerenes, Diels-Alder reactions. This Account highlights recent advances in the molecular design of two-dimensional (2-D) PAHs that combine device performance with environmental stability. New synthetic techniques have been developed to create stable PAHs that extend conjugation in two dimensions. The stability of these novel compounds is consistent with Clar\\'s sextet rule as the 2-D PAHs have greater numbers of sextets in their ground-state configuration than their linear analogues. The ionization potentials (IPs) of nonlinear acenes decrease more slowly with annellation in comparison to their linear counterparts. As a result, 2-D bistetracene derivatives that are composed of eight fused benzene rings are measured to be about 200 times more stable in chlorinated organic solvents than pentacene derivatives with only five fused rings.Single crystals of the bistetracene derivatives have hole mobilities, measured in OFET configuration, up to 6.1 cm2 V-1 s-1, with remarkable Ion/Ioff ratios of 107. The density functional theory (DFT) calculations can provide insight into the electronic structures at both molecular and material levels and to evaluate the main charge-transport parameters. The 2-D acenes with large aspect ratios and appropriate substituents have the potential to provide favorable interstack electronic interactions

单线态分裂的超快光谱学研究∗%Ultrafast sp ectroscopic study for singlet fission

Institute of Scientific and Technical Information of China (English)

张博; 张春峰; 李希友; 王睿; 肖敏

2015-01-01

有机分子中的单线态分裂过程能将单个光激发的单线态激子转化成两个三线态激子。借助此载流子倍增效应，太阳能电池可以更有效地利用太阳光谱中的高能光子，进而突破单结太阳能电池效率的理论极限。因此，单线态分裂备受关注。本文回顾学术界对单线态分裂物理图像的认识以及争议，结合课题组近年来的一些结果，重点总结此领域中运用瞬态光谱学方法取得的实验进展，讨论有关多激子中间暗态机理的不同观点，并介绍单线态分裂材料的发展以及器件应用。%Singlet fission is a spin-allowed process that creates two triplet excitons from one photo-excited singlet exciton in organic semiconductors. This process of carrier multiplication holds the great potential to break the theoretical efficiency limit in single-junction solar cells by making better use of high-energy photons, while capturing lower-energy photons in the usual style. Photovoltaic devices based on singlet fission have achieved external quantum efficiencies in excess of 100%. In this paper, we first introduce the basic concept about singlet fission and review the history of the field briefly. Then, we report some recent advances in the research of singlet fission progress with the combination of our group’s productions. Tetracene and pentacene are chosen as typical polyacene materials for discuss. We describe how scientists make progresses in understanding the underlying physics in singlet fission process. The experimental methods of transient absorption spectra, time-resolved fluorescence spectra and time-resolved two-photon photoemission spectra render numerous results for analysis. Moreover, a survey about the debate on the direct or indirect mechanism with transient optical study is provided. It has been verified that multiexciton state intermediates in singlet fission process and the factors of energy level alignments, intermolecular

Part I: Synthesis and study of nonacene derivatives; Part II: Optoelectronic properties of metal-semiconductor nanocomposites in strongly coupled regime

Science.gov (United States)

Khon, Dmitriy

Acenes are polycyclic aromatic hydrocarbons (PAHs) consisting of linearly fused benzene rings. In the recent past, acenes have been of interest from fundamental and applied perspectives. Smaller acenes such as benzene, naphthalene, and anthracene are among the most studied organic compounds and their properties are well explored. Pentacene has received considerable attention as the most promising active semiconductor for use in organic thin film transistors (TFT) because of its high charge-carrier mobility; however, poor environmental stability is one of the problems limiting its practical application. As the number of rings increases, the members of the acene family become increasingly reactive. The successful synthesis of heptacene developed by Mondal et al. used the Strating-Zwanenberg photodecarbonylation reaction. The lesser stability of the tetracene moieties in the nonacene photoprecursor compared to the anthracene moieties of the heptacene process make its synthesis more challenging. The latter scheme requires 2,3-dibromoanthracene as one of the starting materials. Besides the poor solubility of 2,3-dibromoanthracene, failure was also due to insufficient formation of anthracyne upon treatment of 2,3-dibromoanthracene with n-BuLi. Although the initial idea didn't work we used the same scheme replacing 2,3-dibromoanthracene with 7,8-dibromo-1,4-dihydroanthracene. The reaction of the latter with 5,6,7,8-tetramethylenebicyclo[2.2.2]oct-2-ene gave 1,4,7,8,9,12,15,18,19,20-octadecahydro-8,19-diethenononacene albeit in low yield. Multiple attempts to dehydrogenate the non-aromatic rings using DDQ and other reagents under various conditions failed to produce the desired compound. Recently Miller reported the synthesis of relatively stable heptacene derivatives having a combination of arylthio and o-dialkylphenyl substituents. Miller's scheme used 1,2,4,5-tetrakis(bromomethyl)-3,6-bis(4'- t-butylthiophenyl)benzene as the core precursor. Another synthetic approach