517-51-1Relevant articles and documents
Oxidation of rubrene, and implications for device stability
Ly, Jack T.,Lopez, Steven A.,Lin, Janice B.,Kim, Jae Joon,Lee, Hyunbok,Burnett, Edmund K.,Zhang, Lei,Aspuru-Guzik, Alán,Houk,Briseno, Alejandro L.
, p. 3757 - 3761 (2018/04/12)
The rapid spontaneous photo-oxidation of rubrene to form endo-peroxide, rubrene-Ox1, was monitored via1H NMR and UV-vis spectroscopy. The reaction is thermally reversible, which restores high mobility devices in both the crystalline thin film and single crystal. Prolonged stirring in chlorinated solvents yields a secondary, irreversible product, rubrene-Ox2, which has lost phenol, as confirmed by single crystal analysis. An acid-catalyzed rearrangement of the endo-peroxide to form rubrene-Ox2 was identified here with Density Functional Theory (DFT). Implications of the nature of these processes for the preparation of organic transistors are described.
Rubrene-based single-crystal organic semiconductors: Synthesis, electronic structure, and charge-transport properties
McGarry, Kathryn A.,Xie, Wei,Sutton, Christopher,Risko, Chad,Wu, Yanfei,Young, Victor G.,Bredas, Jean-Luc,Frisbie, C. Daniel,Douglas, Christopher J.
, p. 2254 - 2263 (2013/07/27)
Correlations among the molecular structure, crystal structure, electronic structure, and charge-carrier transport phenomena have been derived from six congeners (2-7) of rubrene (1). The congeners were synthesized via a three-step route from known 6,11-dichloro-5,12-tetracenedione. After crystallization, their packing structures were solved using single-crystal X-ray diffraction. Rubrenes 5-7 maintain the orthorhombic features of the parent rubrene (1) in their solid-state packing structures. Control of the packing structure in 5-7 provided the first series of systematically manipulated rubrenes that preserve the π-stacking motif of 1. Density functional theory calculations were performed at the B3LYP/6-31G(d,p) level of theory to evaluate the geometric and electronic structure of each derivative and reveal that key properties of rubrene (1) have been maintained. Intermolecular electronic couplings (transfer integrals) were calculated for each derivative to determine the propensity for charge-carrier transport. For rubrenes 5-7, evaluations of the transfer integrals and periodic electronic structures suggest these derivatives should exhibit transport characteristics equivalent to, or in some cases improved on, those of the parent rubrene (1), as well as the potential for ambipolar behavior. Single-crystal field-effect transistors were fabricated for 5-7, and these derivatives show ambipolar transport as predicted. Although device architecture has yet to be fully optimized, maximum hole (electron) mobilities of 1.54 (0.28) cm 2 V-1 s-1 were measured for rubrene 5. This work lays a foundation to improve our understanding of charge-carrier transport phenomena in organic single-crystal semiconductors through the correlation of designed molecular and crystallographic changes to electronic and transport properties.
The rubrenic synthesis: The delicate equilibrium between tetracene and cyclobutene
Braga, Daniele,Jaafari, Abdelhafid,Miozzo, Luciano,Moret, Massimo,Rizzato, Silvia,Papagni, Antonio,Yassar, Abderrahim
experimental part, p. 4160 - 4169 (2011/10/01)
Herein we describe the synthesis of new substituted tetraaryltetracenes, obtained by the dimerization of triarylchloroallenes, prepared from propargyl alcohols. The propargyl alcohols were prepared by two different synthetic strategies and then the alcohols were treated to obtain the corresponding acenes. In addition to the expected tetracene derivatives, we observed the formation of bis(alkylidene)cyclobutenes. When strong electron-donating substituents were present, the main product was the cyclobutene. We discuss a reaction mechanism that accounts for the formation of the cyclobutenes.
Rubrenes: Planar and twisted
Paraskar, Abhimanyu S.,Ravikumar Reddy,Patra, Asit,Wijsboom, Yair H.,Gidron, Ori,Shimon, Linda J.W.,Leitus, Gregory,Bendikov, Michael
scheme or table, p. 10639 - 10647 (2009/12/27)
Surprisingly, despite its very high mobility in a single crystal, rubrene shows very low mobility in vacuum-sublimed or solution-processed organic thin-film transistors. We synthesized several rubrene analogues with electron-withdrawing and electron-donating substituents and found that most of the substituted rubrenes are not planar in the solid state. Moreover, we conclude (based on experimental and calculated data) that even parent rubrene is not planar in solution and in thin films. This discovery explains why high mobility is reported in rubrene single crystals, but rubreneshows very low field-effect mobility in thin films. The substituted rubrenes obtained in this work have significantly better solubility than parent rubrene and some even form films and not crystals after evaporation of the solvent. Thus, substituted rubrenes are promising materials for organic light-emitting diode (OLED) applications.
Synthesis process
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Page/Page column 7, (2008/06/13)
A process for synthesizing a naphthacene compound comprises the steps of: (a) reacting a propargyl alcohol compound with a reagent capable of forming a leaving group to form a reaction mixture containing an intermediate; and then (b) heating the intermediate in the presence of a solvent and in the absence of any oxidizing agent and in the absence of any base, to form the naphthacene compound.
Development of a dual-electrolysis stopped-flow method for the observation of electrogenerated chemiluminescence in energy-sufficient systems
Oyama, Munetaka,Okazaki, Satoshi
, p. 5079 - 5084 (2007/10/03)
New methodology for the measurement of electrogenerated chemiluminescence (ECL) has been developed by using a dual-electrolysis stopped-flow system. Using this method, the ECL from 'energy-sufficient' systems composed of different kinds of ion radicals can be easily observed by mixing both the electrolyzed solutions directly. The apparatus and method have been described in detail as well as the ECL observations for various energy-sufficient systems. In particular, in the reaction between the thianthrene (TH) cation radical and the pyrene (PY) anion radical, it was found that the emission spectra changed with the addition of the precursors, reflecting both complex electron- and energy-transfer processes in solution. The present results indicate that the electron- and energy-transfer reactions changed significantly, depending on the type of molecules. The ECL observation with the addition of the third molecule was also informative to compare the ease of the formation of the excited states. It was clarified that the excited states of 9,10-diphenylanthracene and rubrene are easily formed compared with those of TH and PY.
Regioselective Synthesis of Substituted Rubrenes
Dodge, Jeffrey A.,Bain, J. D.,Chamberlin, A. Richard
, p. 4190 - 4198 (2007/10/02)
The development of two complementary synthetic routes to 5,6,11,12-tetraphenylnaphthacene (rubrene) derivatives is described.In one approach, selective nucleophilic addition of aryllithiums to diarylnaphthacenequinones (13, 14, 16), followed by HI aromatization of the corresponding diols, allows for the convenient preparation of a wide variety of selectively functionalized rubrenes.Symmetrically and unsymmetrically di- and tetrasubstituted rubrenes have been prepared, as well as several "end-capped" versions.In a second route, cycloaddition of 1,3-diphenylisobenzofuran with the naphthyne 7 (Ar= Ph) followed by Lewis acid mediated deoxygenation of the resultant oxo-bridged adduct gives rubrene in a particularly convergent manner.Elaboration through the use of substituted isobenzofurans (i.e. 9-11) allows for the analogous preparation of substituted rubrenes (45-47).
Organic Reactive Intermediates: Part VIII - Utility of Triphenylphosphine as Radical Cation Scavenger
Handoo, Kishan L.,Gadru, Kanchan
, p. 995 - 996 (2007/10/02)
Triphenylphosphine reduces a variety of relatively stable radical cations to the parent molecules by a single electron transfer step.The utility of PPh3 as radical cation scavenger can be capitalized in diagnosing mechanisms of radical cation mediated chain reactions.
Photoprocesses in Diphenylpolyenes. 3. Efficiency of Singlet Oxygen Generation from Oxygen Quenching of Polyene Singlets and Triplets
Chattopadhyay, S. K.,Kumar, C. V.,Das, P. K.
, p. 670 - 673 (2007/10/02)
The efficiencies of singlet oxygen (1O2*) photogeneration from the oxygen quenching of the excited states (singlet/triplet) of retinal-related polyenals and diphenylpolyenes have been measured in cyclohexane and methanol by 337.1-nm laser flash photolysis.The 1O2* yields are essentially quantitative with all-trans-retinal and its lower and higher homologues as triplet photosensitizers.For all-trans-1,6-diphenyl-1,3,5-hexatriene (DPH) and all-trans-1,8-diphenyl-1,3,5,7-octatetraene (DPO), both singlet and triplet quenching by oxygen contribute to the formation of 1O2*; significant fractions (0.1-0.7) of the oxygen-induced intersystem crossing in these polyene systems take place without energy transfer to oxygen.The triplet-mediated 1O2* yield obtained by steady-state photolysis of all-trans-1,4-diphenyl-1,3-butadiene (DPB) under energy-transfer sensitization by pyrene-1-aldehyde in O2-saturated benzene is less than unity (0.7 +/- 0.1), suggesting possible fractional quenching by oxygen at an orthogonal geometry of DPB triplet (responsible for "nonproduction" of 1O2*).
