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

Handle URI:
http://hdl.handle.net/10754/564106
Title:
Unconventional, Chemically Stable, and Soluble Two-Dimensional Angular Polycyclic Aromatic Hydrocarbons: From Molecular Design to Device Applications
Authors:
Zhang, Lei; Cao, Yang; Colella, Nicholas S.; Liang, Yong; Bredas, Jean-Luc ( 0000-0001-7278-4471 ) ; Houk, Kendall N.; Briseño, Alejandro L.
Abstract:
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, and correspondingly high carrier mobilities. In stark contrast to the 1-D acenes that form mono- and bis-adducts with fullerenes, 2-D PAHs show less reactivity with fullerenes. The geometry of 2-D PAHs plays a crucial role in determining both the barrier and the adduct stability. The reactivity and stability of the 2-D PAHs with regard to Diels-Alder reactions at different reactive sites were explained via DFT calculations of the reaction kinetics and of thermodynamics of reactions and simple Hückel molecular orbital considerations. Also, because of their increased stability in the presence of fullerenes, these compounds have been successfully used in OPVs. The small-molecule semiconductors highlighted in this Account exhibit good charge-transport properties, comparable to those of traditional linear acenes, while being much more environmentally stable. These features have made these 2-D PAHs excellent molecules for fundamental research and device applications. (Figure Presented). © 2014 American Chemical Society.
KAUST Department:
KAUST Solar Center (KSC); Physical Sciences and Engineering (PSE) Division; Materials Science and Engineering Program
Publisher:
American Chemical Society (ACS)
Journal:
Accounts of Chemical Research
Issue Date:
17-Mar-2015
DOI:
10.1021/ar500278w
Type:
Article
ISSN:
00014842
Sponsors:
Collaboration between the UMass (L.Z., A.L.B.) and Georgia Tech groups (J.L.B.) is supported by the Office of Naval Research awards N000141110636, N0001471410053, and N000141110211. N.S.C. was supported by the Center for Hierarchical Manufacturing, (CMMI-0531171). K.N.H. is grateful to the National Science Foundation (CHE-1059084 and CHE-1361104) for financial support and the Extreme Science and Engineering Discovery Environment (XSEDE) for computer support.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Materials Science and Engineering Program; KAUST Solar Center (KSC)

Full metadata record

DC FieldValue Language
dc.contributor.authorZhang, Leien
dc.contributor.authorCao, Yangen
dc.contributor.authorColella, Nicholas S.en
dc.contributor.authorLiang, Yongen
dc.contributor.authorBredas, Jean-Lucen
dc.contributor.authorHouk, Kendall N.en
dc.contributor.authorBriseño, Alejandro L.en
dc.date.accessioned2015-08-03T12:32:24Zen
dc.date.available2015-08-03T12:32:24Zen
dc.date.issued2015-03-17en
dc.identifier.issn00014842en
dc.identifier.doi10.1021/ar500278wen
dc.identifier.urihttp://hdl.handle.net/10754/564106en
dc.description.abstractPolycyclic 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, and correspondingly high carrier mobilities. In stark contrast to the 1-D acenes that form mono- and bis-adducts with fullerenes, 2-D PAHs show less reactivity with fullerenes. The geometry of 2-D PAHs plays a crucial role in determining both the barrier and the adduct stability. The reactivity and stability of the 2-D PAHs with regard to Diels-Alder reactions at different reactive sites were explained via DFT calculations of the reaction kinetics and of thermodynamics of reactions and simple Hückel molecular orbital considerations. Also, because of their increased stability in the presence of fullerenes, these compounds have been successfully used in OPVs. The small-molecule semiconductors highlighted in this Account exhibit good charge-transport properties, comparable to those of traditional linear acenes, while being much more environmentally stable. These features have made these 2-D PAHs excellent molecules for fundamental research and device applications. (Figure Presented). © 2014 American Chemical Society.en
dc.description.sponsorshipCollaboration between the UMass (L.Z., A.L.B.) and Georgia Tech groups (J.L.B.) is supported by the Office of Naval Research awards N000141110636, N0001471410053, and N000141110211. N.S.C. was supported by the Center for Hierarchical Manufacturing, (CMMI-0531171). K.N.H. is grateful to the National Science Foundation (CHE-1059084 and CHE-1361104) for financial support and the Extreme Science and Engineering Discovery Environment (XSEDE) for computer support.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleUnconventional, Chemically Stable, and Soluble Two-Dimensional Angular Polycyclic Aromatic Hydrocarbons: From Molecular Design to Device Applicationsen
dc.typeArticleen
dc.contributor.departmentKAUST Solar Center (KSC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentMaterials Science and Engineering Programen
dc.identifier.journalAccounts of Chemical Researchen
dc.contributor.institutionDepartment of Polymer Science and Engineering, University of MassachusettsAmherst, MA, United Statesen
dc.contributor.institutionDepartment of Chemistry and Biochemistry, University of CaliforniaLos Angeles, CA, United Statesen
dc.contributor.institutionDepartment of Chemical and Biomolecular Engineering, University of CaliforniaLos Angeles, CA, United Statesen
kaust.authorBredas, Jean-Lucen
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