Exciplex emission

This emission occurs at longer wavelengths than the normal fluorescence. The exciplex emission, on the other hand, occurs from an excited associated complex formed between an excited species and a different ground-state species. 

X. Jiang, M.S. Liu, and A.K.-Y. Jen, Bright and efficient exciplex emission from light-emitting diodes based on hole-transporting amine derivatives and electron-transporting polyfluorenes, J. Appl. Phys., 91 10147-10152 (2002). 

LC Palilis, AJ Makinen, M Uchida, and ZH Kafafi, Highly efficient molecular organic light-emitting diodes based on exciplex emission, Appl. Phys. Lett., 82 2209-2211, 2003. 

The chemical association of the exciplex results from an attraction between the excited-state molecule and the ground-state molecule, brought about by a transfer of electronic charge between the molecules. Thus exciplexes are polar species, whereas excimers are nonpolar. Evidence for the charge-transfer nature of exciplexes in nonpolar solvents is provided by the strong linear correlation between the energy of the photons involved in exciplex emission and the redox potentials of the components. 

The exciplex emission is also affected by solvent polarity, where an increase in the solvent polarity results in a lowering of the energy level of the exciplex, at the same time allowing stabilisation of charged species formed by electron transfer (Figure 6.7). Thus, in polar solvents the exciplex emission is shifted to even higher wavelength and accompanied by a decrease in the intensity of the emission, due to competition between exciplex formation and electron transfer. 

In other white light devices, blue, green and red emitters are combined. Kido et al. [169, 170] designed multilayer systems using 6 (TPD) for blue, metal-chelate complexes for green and red emission, respectively. Similar devices have been developed by other groups, using Forster transfer or exciton confinement for the creation of the three primary colors [171, 172]. Exciplex emission was... 

The exciplex intensity showed quite different behavior as the setting proceeded. A comparison of the (monomer peak/monomer peak) ratio to the (exciplex peak/monomer peak) ratio was quite illuminating. We considered the initial maximum wavelength of the exciplex emission at 540 nm, and compared its intensity to the monomer intensity at 405 nm as the dissolution/ polymerization proceeded. A substantial decrease in exciplex intensity, compared to monomer intensity, was observed over the first 40 min of the cure. The ratio then leveled off, indicating that the local viscosity had reached a maximum after 40 min and that the dissolution/polymerization was considered to have reached completion at the ambient temperature of the laboratory. Since the working time for the cement was considerably less than the 40-min time period over which the exciplex/monomer intensity ratio was steadily decreasing, the intensity ratios served as in situ monitors of the cure. 

The effect of exciplex dissociation (process MC) on the over-all kinetics of molecular fluorescence decay has been examined by Ware and Richter34 for the system perylene-dimethylaniline in solvents with dielectric constants (e) varying from 2.3 to 37. In low dielectric media (e = 2.3-4) the perylene fluorescence response may be fitted to a two-component exponential curve and exciplex emission is also observed, whereas in more polar solvents (e > 12) exciplex fluorescence is absent (at ambient temperatures) and the molecular fluorescence decays exponentially. These observations are consistent with both an increase in exciplex stability toward molecular dissociation with solvent polarity (Eq. 13) and the increased probability of dissociation into solvated ions... 

ECL emission has been also observed in the mixed ECL systems involving PAHs with reaction partners like aromatic amines or ketones forming radical cations D + or radical anions A-, respectively.114127 Such approach solves the problems caused by the instability of ECL reactants but lowers distinctly the free energy available for the formation of an excited state. Usually, the energy released in electron transfer between A- + D + ions is insufficient to populate emissive 11A or D states directly and the annihilation of the radical ions usually generates only nonemissive3 A or 3 D triplets that produce light via triplet-triplet annihilation. Consequently ECL efficiencies in the mixed ECL systems are usually very low. Only in some cases, when radiative electron transfer between A + D+ species is operative, relatively intense [A D + ] exciplex emission can be observed. 

Figure 6.8 Temperature dependence of fluorescence emission from 9-methoxy-10-phenanthrenecarboxanil. Exciplex emission and isoemissive point.

In polar solvents such as chloroform, dichloromethane, acetone, and acetonitrile, the fluorescence quantum yields of 97a-d decrease by varying degrees (see Table 19). Moreover, in the case of the phenyl and acetyl derivatives 97c and 97d, the rather drastic decrease of the structured fluorescence from the locally excited anthracene is associated with the appearance of a structureless, red-shifted emission which is attributable to an intramolecular exciplex. For 97d, in which the electron acceptor properties of the aromatic carbonyl moiety are enhanced by p-acetyl substitution, exciplex emission is dominant even in toluene solution (see Figure 22). 

In polar solvents, the quantum yields for the emission from the locally excited state of anthronyl-anthracenes 98 and 99 decrease drastically (see Tables 20 and 21), and a structureless, red-shifted exciplex emission is observed (see Figure 23). For the parent compound 98a in dichloromethane, for example, the quantum yield of emission from the exciplex state is 0.012, but that of emission from the locally excited state has decreased to 0.00058 (cf. Tables 20 and 22). Thus, intramolecular exciplex formation between the photoexcited anthracene moiety and the aromatic ketone in its electronic ground state represents the major mode of deactivation in polar solvents. 

TABLE 23 Solvent Dependent Quantum Yields of Exciplex Emission for 101a and... 

Including overlapping exciplex emission. hExciplex emission not included. 

Figure 4.23 Orbital interactions in exciplex formation between an excited molecule M (electron donor) and a ground state molecule N. hvexp is the exciplex emission...

In 1977, Scharf and Mattay [123] found that benzene undergoes ortho as well as meta photocycloaddition with 2,2-dimethyl-1,3-dioxole and, subsequently, Leismann et al. [179,180] reported that they had observed exciplex fluorescence from solutions in acetonitrile of benzene with 2,2-dimethyl-l,3-dioxole, 2-methyl-l,3-dioxole, 1,3-dioxole, 1,4-dioxene, and (Z)-2,2,7,7-tetram-ethyl-3,6-dioxa-2,7-disilaoct-4-ene. The wavelength of maximum emission was around 390 nm. In cyclohexane, no exciplex emission could be detected. No obvious correlation could be found among the ionization potentials of the alkenes, the Stern-Volmer constants of quenching of benzene fluorescence, and the fluorescence emission energies of the exciplexes. Therefore, the observed exciplexes were characterized as weak exciplexes with dipole-dipole rather than charge-transfer stabilization. Such exciplexes have been designated as mixed excimers by Weller [181],... 

A kinetic scheme was proposed [122] with the fluorescent exciplex as precursor of the photoproducts (ortho as well as meta adducts). Quantum yields of adduct formation, exciplex emission, and benzene fluorescence were measured as a function of alkene concentration. The kinetic data fit the proposed reaction scheme. The authors have also attempted to prove the intermediacy of the exciplex in the photoaddition by adding a quencher to the system benzene + 2,2-dimethyl-... 

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