Perylene, excitation transfer from

For the excited singlet state of rhodamine as product state the free energy plot of the reverse electron transfer from the reduced dye to the hole (dashed curve in Fig. 31) is a mirror image to the free energy plot of the forward reaction relative to AG° =0. We immediately see from Figs. 31 and 32 that this reverse reaction is very fast at phenanthrene and slower at chrysene. It is still slower at anthracene and extremely slow at perylene. At phenanthrene this reverse reaction can compete with the dissociation of the hole from the reduced dye as is borne out by the recombination controlled current in this system (Fig. 27). 

Fig. 12. Perrin quenching radii, R, [33J vs. variations of the free energy, - AG°, of electron transfer from the excited donor molecule to the acceptor molecule for donor-acceptor pairs in vitreous /nms-l,5-decalindiol. 1, Rubrene + A/ AT-diethylamline (DEA) 2, rubrene + N,N,-Ar,Ar-tetramethyl-p-phenylenediamine (TMPD) 3, rubrene + tetrakis(dimethylaminoethy-lene) 4, tetracene + DEA 5, tetracene + TMPD 6, 9,10-dinaphthylanthracene + DEA 7, 9,10-dinaphthylanthracene + TMPD 8, perylene + DEA 9, perylene + TMPD 10, 9-methylanthracene + TMPD 11, 9,10-diphenylanthracene + TMPD 12, coronene + TMPD 13, benzo[ Ai jperylene + TMPD 14, fluoranthene + DEA 15, acridine + DEA.

In several cases, dependent on the donor, the electron transfer triplet energy transfer from the triplet state of the fullerenes to the donor was observed. For example, excitation of C6o/perylene (Pe) mixtures leads to 3Pe and C6o in a fast reaction ((1.4 0.1) X 109 M 1 s-1). The electron transfer from Pe to 3C o occurs with a rate one-third of triplet energy transfer [127]. Ito et al. investigated the photoexcitation of mixed system of C6o and (3-carotene [141], They observed triplet energy transfer from 3C o to (3-carotene in polar as well as in nonpolar solvents besides electron transfer from (3-carotene to 3C o However, the electron transfer rate constant increases with solvent polarity while the energy transfer is only less effected by the change of solvent polarity (Table 5). 

Further work used a similar system to inhibit the formation of a second ion pair completely, using the electric field of an initial ion pair. In compound 14, Zn3PN and 9-(N-pyrrolidinyl)perylene-3,4-dicarboximide (pyr-PMI) are the electron donors, while NI and PI are once again electron acceptors.11701 Photoinduced electron transfer from Zn3PN to PI with 416 nm laser pulses occurs with t = 27 ps however, if a 645 nm laser pulse is used to excite pyr-PMI first, this event is completely inhibited. 

Various compounds were shown to sensitize the photochemical decomposition of pyridinium salts. Photolysis of pyridinium salts in the presence of sensitizers such as anthracene, perylene and phenothiazine proceeds by an electron transfer from the excited state sensitizer to the pyridinium salt. Thus, a sensitizer radical cation and pyridinyl radical are formed as shown for the case of anthracene in Scheme 15. The latter rapidly decomposes to give pyridine and an ethoxy radical. Evidence for the proposed mechanism was obtained by observation of the absorption spectra of relevant radical cations upon laser flash photolysis of methylene chloride solutions containing sensitizers and pyridinium salt [64]. Moreover, estimates of the free energy change by the Rehm-Weller equation [65] give highly favorable values for anthracene, perylene, phenothiazine and thioxanthone sensitized systems, whilst benzophenone and acetophenone seemed not to be suitable sensitizers (Table 5). The failure of the polymerization experiments sensitized by benzophenone and acetophenone in the absence of a hydrogen donor is consistent with the proposed electron transfer mechanism. 

In other copolymers the lower-energy unit acts as a trap so that the emission comes solely from it, rather than from an excited state spread along the chain, as in the above examples. Thus Mullen and coworkers [123] have prepared copolymers of fluorene containing low (1-5 mol %) perylene-based dye chromophores in which the emission comes solely from the dye units due to a combination of efficient Forster energy transfer from the fluorene units and charge trapping on the dyes. By varying the nature of the incorporated chromophore they were able to tune the emission color across the whole visible spectrum. 

This salt can also be activated by various photosensitizer [114—116] such as perylene anthracene and phenothiazine. The mechanism involves again an electron transfer from the excited sensitizer to the ground-state phenacyl salt (Scheme 11.31). 

Two typical dye molecules. The europium complex (a) transfers absorbed light to excited-state levels of the complexed Eu , from which lasing occurs. The perylene molecule (b) converts incident radiation into a triplet state, which decays slowly and so allows lasing to occur. 

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>. 

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