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Title: Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach

Abstract

Density functional theory calculations were carried out to investigate the evolvement of charge transport properties of a set of new discotic systems as a function of ring and heteroatom (B, Si, S, and Se) substitution on the basic structure of perylene. The replacement of six-membered rings by five-membered rings in the reference compound has shown a prominent effect on the electron reorganization energy that decreases ∼0.2 eV from perylene to the new carbon five-membered ring derivative. Heteroatom substitution with boron also revealed to lower the LUMO energy level and increase the electron affinity, therefore lowering the electron injection barrier compared to perylene. Since the rate of the charge transfer between two molecules in columnar discotic systems is strongly dependent on the orientation of the stacked cores, the total energy and transfer integral of a dimer as a disc is rotated with respect to the other along the stacking axis have been predicted. Aimed at obtaining a more realistic approach to the bulk structure, the molecular geometry of clusters made up of five discs was fully optimized, and charge transfer rate and mobilities were estimated for charge transport along a one dimensional pathway. Heteroatom substitution with selenium yields electron transfer integralmore » values ∼0.3 eV with a relative disc orientation of 25°, which is the preferred angle according to the dimer energy profile. All the results indicate that the tetraselenium-substituted derivative, not synthetized so far, could be a promising candidate among those studied in this work for the fabrication of n-type semiconductors based on columnar discotic liquid crystals materials.« less

Authors:
; ; ; ;  [1];  [2]
  1. Departamento de Química Física y Analítica, Universidad de Jaén, Campus Las Lagunillas, E23071 Jaén (Spain)
  2. Instituto de Energía Solar and Departamento TFB, E.T.S.I. Telecomunicación, Universidad Politécnica de Madrid, Ciudad Universitaria, Madrid 28040 (Spain)
Publication Date:
OSTI Identifier:
22678974
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 145; Journal Issue: 5; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHARGE TRANSPORT; DENSITY FUNCTIONAL METHOD; ELECTRON BEAM INJECTION; ELECTRON TRANSFER; ENERGY LEVELS; EXPERIMENTAL DATA; LIQUID CRYSTALS; PERYLENE

Citation Formats

Navarro, Amparo, E-mail: anavarro@ujaen.es, Fernández-Liencres, M. Paz, Peña-Ruiz, Tomás, Granadino-Roldán, José M., Fernández-Gómez, Manuel, and García, Gregorio. Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach. United States: N. p., 2016. Web. doi:10.1063/1.4960051.
Navarro, Amparo, E-mail: anavarro@ujaen.es, Fernández-Liencres, M. Paz, Peña-Ruiz, Tomás, Granadino-Roldán, José M., Fernández-Gómez, Manuel, & García, Gregorio. Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach. United States. doi:10.1063/1.4960051.
Navarro, Amparo, E-mail: anavarro@ujaen.es, Fernández-Liencres, M. Paz, Peña-Ruiz, Tomás, Granadino-Roldán, José M., Fernández-Gómez, Manuel, and García, Gregorio. Sun . "Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach". United States. doi:10.1063/1.4960051.
@article{osti_22678974,
title = {Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach},
author = {Navarro, Amparo, E-mail: anavarro@ujaen.es and Fernández-Liencres, M. Paz and Peña-Ruiz, Tomás and Granadino-Roldán, José M. and Fernández-Gómez, Manuel and García, Gregorio},
abstractNote = {Density functional theory calculations were carried out to investigate the evolvement of charge transport properties of a set of new discotic systems as a function of ring and heteroatom (B, Si, S, and Se) substitution on the basic structure of perylene. The replacement of six-membered rings by five-membered rings in the reference compound has shown a prominent effect on the electron reorganization energy that decreases ∼0.2 eV from perylene to the new carbon five-membered ring derivative. Heteroatom substitution with boron also revealed to lower the LUMO energy level and increase the electron affinity, therefore lowering the electron injection barrier compared to perylene. Since the rate of the charge transfer between two molecules in columnar discotic systems is strongly dependent on the orientation of the stacked cores, the total energy and transfer integral of a dimer as a disc is rotated with respect to the other along the stacking axis have been predicted. Aimed at obtaining a more realistic approach to the bulk structure, the molecular geometry of clusters made up of five discs was fully optimized, and charge transfer rate and mobilities were estimated for charge transport along a one dimensional pathway. Heteroatom substitution with selenium yields electron transfer integral values ∼0.3 eV with a relative disc orientation of 25°, which is the preferred angle according to the dimer energy profile. All the results indicate that the tetraselenium-substituted derivative, not synthetized so far, could be a promising candidate among those studied in this work for the fabrication of n-type semiconductors based on columnar discotic liquid crystals materials.},
doi = {10.1063/1.4960051},
journal = {Journal of Chemical Physics},
number = 5,
volume = 145,
place = {United States},
year = {Sun Aug 07 00:00:00 EDT 2016},
month = {Sun Aug 07 00:00:00 EDT 2016}
}
  • An analysis of the results of theoretical and physicochemical studies of and x-ray diffraction data for a series of aminovinyl ketones - derivatives of hydroxy aldehydes of benzo(b)-annelated five-membered heterosystems - is presented. In addition to the peculiarities of the aminovinyl ketone fragment, the effect of the heteroatom of the five-membered ring on the structure and properties of aminovinyl ketones, which consists in direct electronic conjugation of the ring carbonyl group with the heteroatom, was ascertained.
  • The electronic structures of C{sub 60} derivatives with one to five atoms added at adjacent double bonds radiating from a five-membered ring have been calculated with the PM-3 parametrization of the MNDO Hamiltonian. The calculations were done for n = 1-4 with H, F, and Cl and for n=5 with H. The stabilities of the C{sub 60} derivatives are predicted from the calculated energies. The isodesmic reactions of C{sub 60} with alkanes and perchloralkanes are predicted to become more exothermic with increase in the number of substituents and the length of the alkyl chain. The reactions of C{sub 60} withmore » perfluoralkanes are not predicted to be exothermic due to the stable C-F bond in perfluoralkanes. Valence bond structures are presented on the basis of the calculated geometries and spin densities. These results are compared to ESR measurements. 40 refs., 10 figs., 3 tabs.« less
  • The results obtained by the MINDO/3 method for all the oxo derivatives of five-membered saturated heterocycles are shown here to be in better agreement with the experimental ionization potentials and more accurately describe the orbital energies and the structure of the highest occupied MO's than do the results obtained by the CNDO/2 and MNDO methods. The decisive role of the inductive effect of the heteroatoms introduced into the cyclopentanone molecule and of a carbonyl group introduced into the molecules of the original heterocycles on the first ionization potentials of their oxo derivatives has been demonstrated.
  • The synthesis and characterizations of some new eta/sup 5/-heterocyclic manganese tricarbonyl complexes are described. Kinetic studies are reported for CO substitution reactions of these nitrogen family eta/sup 5/-dimethylheterocyclic manganese tricarbonyl complexes. The results show that only the N-heterocycle compounds undergo CO substitution by phosphorus nucleophiles. These results are attributed to the greater electronegativity of N than that of C, P, or As. Both tricarbonyl(eta/sup 5/-3,4-dimethylpyrrolyl)manganese(I) and tricarbonyl(eta/sup 5/-2,5-dimethylpyrrolyl)manganese(I) substitute CO by an associative pathway in which the reaction rates are first order in concentration of metal complex and first order in concentration of entering nucleophile. The former compound also substitutesmore » CO by a pathway that is independent of the concentration of incoming nucleophile. The second-order pathway is believed to involve a ring-slippage (eta/sup 5/ ..-->.. eta/sup 3/ ..-->.. eta/sup 5/) mechanism, whereas the first order pathway appears to involve a ligand-dissociation mechanism.« less