Rubrene

Using a stable dopant as the emissive dye has been shown to greatly enhance the lifetime of small molecule LEDs. Rubrene doped into the Alq, electron transport layer ] 184] or into the TPD hole transport layer 1185] can extend the lifetime by an order of magnitude. Similarly, dimclhylquinacridone in Alq has a beneficial effect ]45 ]. The likely mechanism responsible for this phenomenon is that the dopant acts as a trap for the excilon and/or the charge. Thus, molecules of the host maLrix are in their excited (cationic, anionic or cxcitonic) states for a smaller fraction of the time, and therefore have lower probability to undergo chemistry. 

Fluorescent small molecules are used as dopants in either electron- or hole-transporting binders. These emitters are selected for their high photoluminescent quantum efficiency and for the color of their emission. Typical examples include perylene and its derivatives 44], quinacridones [45, penlaphenylcyclopenlcne [46], dicyanomethylene pyrans [47, 48], and rubrene [3(3, 49]. The emissive dopant is chosen to have a lower excited state energy than the host, such that if an exciton forms on a host molecule it will spontaneously transfer to the dopant. Relatively small concentrations of dopant are used, typically in the order of 1%, in order to avoid concentration quenching of their luminescence. 

A particularly elegant example of cluster formation involving chiral recognition and retention of chirality through an increasingly complex hierarchical series of clusters is that of rubrene on Au l 1 1 [9] illustrated in Figure 1.5... 

Figure 1.5 (a) Hierarchy of clusters of rubrene on Au l 1 1, showing the evolution from trimers to pentamers of trimers and eventually 150 molecules per cluster as a decamer of the pentamers. (b) Illustration ofthe preservation of chirality through the hierarchy. (Adapted with permission from Ref. [9]). 

Figure 12.1.7 The molecular structure of rubrene (5,6,11,12-tetraphenyl-naphthacene).

DPA) in dimethylphthalate at about 70°, yields a relatively strong blue Umax =435 nm) chemiluminescence the quantum yield is about 7% that of luminol 64>. The emission spectrum matches that of DPA fluorescence so that the available excitation energy is more than 70 kcal/mole. Energy transfer was observed on other fluorescers, e.g. rubrene and fluorescein. The mechansim of the phthaloyl peroxide/fluorescer chemiluminescence reaction very probably involves radicals. Luminol also chemiluminesces when heated with phthaloyl peroxide but only in the presence of base, which suggests another mechanism. The products of phthaloyl peroxide thermolysis are carbon dioxide, benzoic acid, phthalic anhydride, o-phenyl benzoic acid and some other compounds 65>66>. It is not yet known which of them is the key intermediate which transfers its excitation energy to the fluorescer. 

As reported by T. Wilson 71>, the emitter is the anthracene derivative 9 which can be replaced by rubrene, but not by 9.10-diphenylanthracene. 

As mentioned in Section II. C., the concerted bond cleavage of 1.2-dioxetane derivatives has been proposed to be of general importance in respect of the excitation step of a large number of chemiluminescence reactions. The first experimental results concerning simple dioxetanes were obtained by M. M. Rauhut and coworkers in their work on activated oxalic ester chemiluminescence 24>. From experimental data on the reaction of e.g. bis (2.4-dinitrophenyl)oxalate with hydrogen peroxide in the presence of rubrene, they concluded that 1.2-dioxetanedione... 

The quantum yield in the reaction between rubrene radical ions was found to be in the range 0.008.... 0.015, depending on whether the radical anion or the radical cation was produced first 144>. The latter is, in general, less stable. 

The electrogenerated radical anions of aromatic hydrocarbons, e.g. DPA, rubrene, fluorene, can also act as reductants towards electro-chemically obtained radical cations which are derivatives of other aromatic compounds such as N,N-dimethyl-/>-phenylenediamine (Wurster s red) 150> (see Section VIII. B.). When a mixture of DPA and a halide such as 99 (DPACI2) or 100 is electrolysed, a bright chemiluminescence is observed the quantum yields are about two orders of magnitude higher than that of the DPA radical anion-radical cation reaction 153>. 

Chemiluminescence also occurs during electrolysis of mixtures of DPACI2 99 and rubrene or perylene In the case of rubrene the chemiluminescence matches the fluorescence of the latter at the reduction potential of rubrene radical anion formation ( — 1.4 V) at —1.9 V, the reduction potential of DPA radical anion, a mixed emission is observed consisting of rubrene and DPA fluorescence. Similar results were obtained with the dibromide 100 and DPA and/or rubrene. An energy-transfer mechanism from excited DPA to rubrene could not be detected under the reaction conditions (see also 154>). There seems to be no explanation yet as to why, in mixtures of halides like DPACI2 and aromatic hydrocarbons, electrogenerated chemiluminescence always stems from that hydrocarbon which is most easily reduced. A great number of aryl and alkyl halides is reported to exhibit this type of rather efficient chemiluminescence 155>. 

Olas and Wachowicz (2002) investigated the effects of tranx-resveratrol and vitamin C on oxidative stress in blood platelets. The level of 02 in control blood platelets and platelets incubated with resveratrol or vitamin C was recorded using a chemiluminescence method. On the other hand, Oh and others (2006) reported the x02 quenching activities of various freshly squeezed fruit and vegetable juices by measuring their inhibitory effects on the rubrene oxidation induced by x02 from disproportionation of hydrogen peroxide by sodium molybdate in a microemulsion system. 

Polyaromatic hydrocarbons Synthetic 10"5-10"7 mol L"1 (anthracene, rubrene, pyrene)... 

While it is in the triplet state a molecule may undergo typical diradical reactions. This provides a plausible mechanism for radical-like reactions of substances that are largely diamagnetic. They are partly converted to the triplet state by light, or in the case of low lying triplet states, by heat. Probable examples of this mechanism are the photooxidation of rubrene and the photooxidation and dimerization of anthracene and higher members of the acene series.76... 

On heating, rubrene peroxide gives up most of its oxygen to regenerate rubrene. 

The explanation for these diradical reactions can not be quite so simple as the one hinted at above however, since the quantum yield of rubrene peroxide does not appear to depend only on the concentration of photoactivated rubrene triplet molecules but also on the concentrations of rubrene itself and of oxygen.77... 

Stingelin-Stutzmann, N. Smits, E. Wondergem, H. Tanase, C. Blom, P. Smith P. De Leeuw, D. 2005. Organic thin-film electronics from vitreous solution-processed rubrene hypereutectics. Nature Mater. 4 601-606. 

By optimization of device structures and by using different hole and electron injection or transport materials, Chen et al. achieved an excellent red OLED with a very high efficiency based on the DCJTB molecule. The OLED structure is glass (0.7 mm)/SiO2(20 nm) ITO/CFx/NPD(l 10 nm)/Alq3 5% rubrene 2%DCJTB(30 nm)/Alq3(55 nm)/LiF(0.1... 

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