Electron perylene

Decomposition of diphenoylperoxide [6109-04-2] (40) in the presence of a fluorescer such as perylene in methylene chloride at 24°C produces chemiluminescence matching the fluorescence spectmm of the fluorescer with perylene was reported to be 10 5% (135). The reaction follows pseudo-first-order kinetics with the observed rate constant increasing with fluorescer concentration according to = k [flr]. Thus the fluorescer acts as a catalyst for peroxide decomposition, with catalytic decomposition competing with spontaneous thermal decomposition. An electron-transfer mechanism has been proposed (135). 

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. 

The electron transfer between an electrochemically produced perylene dianion and a C02 molecule was also suggested by cyclic voltammetry in a DMF solution.161 Later, perylene was used162 in the photochemical fixation of C02, as a nonmetal electron carrier to C02. 

Tazuke and Kitamura162 reported the first example of an artificial photosynthetic system based on electron transport sensitization, although the product was not a hydrocarbon, but rather formic acid. Their system is shown schematically in Fig. 17. In this system, the photochemically generated singlet excited state of an aromatic hydrocarbon, such as pyren (Py) or perylene (Pe), was... 

It is also possible to form radical cations and radical anions on the same alumina or silica-alumina surface (88). One of the more interesting observations was that a marked enhancement of the radical anion spectrum for trinitrobenzene results when perylene is adsorbed on an alumina surface, and similarly the radical cation signal is reenforced by adsorption of trinitrobenzene. The linewidths of the spectra confirm that the radical ions are separated by a distance greater than 10 A. This means that the electron must be transfered through the lattice or that the ions separate after the transfer step, which seems unlikely. Oxygen was still required for the formation of the radical cation. 

This list includes BP, 7,12-dimethylbenz[a]anthracene, 3-methylchol-anthrene, dibenzo[a,i]pyrene and dibenzo[a,h]pyrene. These PAH can be activated both by one-electron oxidation and/or monooxygenation. There are a few PAH with low IP which are inactive (Table I), such as perylene, or weakly active, such as anthanthrene. This indicates that low IP is a necessary, but not sufficient factor for determining carcinogenic activity by one-electron oxidation. These inactive or weakly active PAH have the highest density of positive charge delocalized over several aromatic carbon atoms in their radical cations, whereas the active PAH with low IP have charge mainly localized on one or a few carbon atoms in their radical cations. 

Thus, from equation (63), the magnitude of the electronic coupling matrix element may finally be estimated, leading to values of 21 and 24 meV for EDA and perylene, respectively. That these values are quite reasonable derives from the observation that they correspond to moderately non-adiabatic electron transfer at the ground state (with electronic factors of 2 /(1 + P) - 0.5 and 0.6 with EDA and perylene, respectively). 

Although organic anion radicals are oxygen sensitive, they have been isolated as crystalline salts from a variety of electron acceptors (e.g., chloranil, tetracyanoethylene, tetracyanoquinodimethane, perylene, naphthalene, anthracene, tetraphenylethylene, etc.) and their structures have been established by X-ray crystallography.180... 

Li C, Mishchenko A, Li Z, Pobelov I, Wandlowski T, Li XQ, Wurthner F, Bagrets A, Evers F (2008) Electrochemical gate-controlled electron transport of redox-active single perylene bisimide molecular junctions. J Phys Condens Matter 20 374122... 

Optical properties of dendrimers bearing eight chromophores have been examined by single molecule spectroscopy techniques. It is especially exciting that variations in the spectra are recorded if one of these dendrimers is observed for a period of time under continuous irradiation.1481 The fluorescence intensity of the dendrimer nanoparticle also jumps between discrete emissive levels. All these findings suggest the existence of strong electronic interactions between several perylene imide chromophores within one dendrimer and provide new... 

Optical and Electronic Properties of the Fluorene-Perylene Copolymers... 

Attaching perylene moieties as side groups allows achievement of high concentration without affecting the electronic structure of the polymer backbone. Putting 16% perylene moieties as side chains predictably results in more efficient energy transfer, observed with polymer 360, both in solution and solid state (emission band at 599 nm). Although no PLED device with 360 has been reported, this material showed excellent performance in solar cells (external photovoltaic QE = 7%, in blend with PPV) [434]. 

It is now well established that when a surface presents electron donor or electron acceptor sites, it is possible to ionize molecules of relatively high electron affinity (> 2 eV) or low ionization potential values, resulting in paramagnetic radical ions. For instance anthracene and perylene are easily positively ionized on alumina (7 ) (IP = 7.2 and 6.8 eV respectively). The adsorption at room temperature of benzenic solution of perylene, anthracene and napthalene on H-ZSM-5 and H-ZSM-11 samples heated up to 800°C prior to adsorption did not give rise to the formation of the corresponding radical cation. For samples outgassed at high... 

Quite differently, Pleux et al. tested a series of three different organic dyads comprising a perylene monoimide (PMI) dye linked to a naphthalene diimide (NDI) or C60 for application in NiO-based DSSCs (Fig. 18.7) [117]. They corroborated a cascade electron flow from the valance band of NiO to PMI and, finally, to C60. Transient absorption measurements in the nanosecond time regime revealed that the presence of C60 extends the charge-separated state lifetime compared to just PMI. This fact enhanced the device efficiencies up to values of 0.04 and 0.06% when CoII/m and P/Ij electrolytes were utilized, respectively. More striking than the efficiencies is the remarkable incident photon-to-current efficiency spectrum, which features values of around 57% associated to photocurrent densities of 1.88 mA/cm2. 

Fig. 11 One-dimensional electron density projection along the c-axis for a perylene dye intercalated in an Mg/Al LDH and a structural model based on this data. Reprinted with permission from [150]. Copyright Wiley...

It is clear that deuterium as a substituent has the electron-donating effect. In other words, it can decrease electron affinity of the whole molecule. Potentials of reversible one-electron reduction for naphthalene, anthracene, pyrene, perylene, and their perdeuteriated counterparts indicate that the counterparts exhibit slightly more negative potentials (Goodnow and Kaifer 1990, Morris and Smith 1991). For example, the measurable differences in the reduction potentials are equal to -13 mV for the pair of naphthalene-naphthalene-dj or -12 mV for the pair of anthracene-anthracene-djo. The possible experimental error does not exceed 2 mV (Morris and Smith 1991). In another example, in DMF with 0.1 M n-Bu4NPFg, the deuterated pyrenes were invariably found to be more difficult to reduce than pyrene itself. The largest difference observed, 12.4 mV, was between perdeuteriated pyrene and pyrene bearing no deuterium at all with standard deviations between 0.2 and 0.4 mV (Hammerich et al. 1996). 

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