Pyrene excimer emission

In a film, however, molecular mobility is severely limited, so that excimer fluorescence must arise mainly from pairs or groups of pyrene molecules that were approximately in the excimer configuration when the film was cast. Thus, the intensity of the excimer emission is also an indication of the local concentration of pyrene in the cast film. If the pyrene aggregates, we expect that the excimer fluorescence would increase with aggregation. This system can be used to look at the aggregation of very low concentrations of a small molecule dye in a polymer film, and potentially detect molecular aggregation before it would be observable by other tech-... 

Yang JS, Lin CS, Hwang CY (2001) Cu2+-induced blue shift of the pyrene excimer emission a new signal transduction mode of pyrene probes. Org Lett 3 889-892... 

A first generation poly(amido amine) dendrimer has been functionalized with three calyx[4]arenes, each carrying a pyrene fluorophore (4) [30]. In acetonitrile solution the emission spectrum shows both the monomer and the excimer emission band, typical of the pyrene chromophore. Upon addition of Al3+ as perchlorate salt, a decrease in the excimer emission and a consequent revival of the monomer emission is observed. This can be interpreted as a change in the dendrimer structure and flexibility upon metal ion complexation that inhibits close proximity of pyrenyl units, thus decreasing the excimer formation probability. 1H NMR studies of dendrimer 4 revealed marked differences upon Al3+ addition only in the chemical shifts of the CH2 protons linked to the central amine group, demonstrating that the metal ion is coordinated by the dendrimer core. MALDI-TOF experiments gave evidence of a 1 1 complex. Similar results have been obtained for In3+, while other cations such as Ag+, Cd2+, and Zn2+ do not affect the luminescence properties of... 

E-3 (Figure 10.26) is the first example of an ionophoric calixarene with appended fluorophores, demonstrating the interest in this new class of fluorescent sensors. The lower rim contains two pyrene units that can form excimers in the absence of cation. Addition of alkali metal ions affects the monomer versus excimer emission. According to the same principle, E-4 was designed for the recognition of Na+ the Na+/K+ selectivity, as measured by the ratio of stability constants of the complexes, was indeed found to be 154, while the affinity for Li+ was too low to be determined. 

Modification of PAA/Au grafts with the amine and alcohol functionalized pyrenes 2 and 3 produced highly fluorescent films [23]. These deriva-tized films exhibited both monomer and excimer fluorescence. The relative amounts of monomer and excimer emission depended on the pyrene concentration used in the derivatization process. When modest concentrations... 

Fig. 46 Pyrene monomer and excimer decay profiles in SDS micellar solutions [SDS] = 8.2 X 10 kmolm , [NaCl] = 10 kmolm , CMC = 1.5 x 10" kmolm", pyrene levels are indicated as the ratio of micellized SDS to added pyrene emission monitored at 383 nm for monomer and 480 nm for excimer. (A) Monomer emission for SDS/Py = 2160, (B) monomer emission for SDS/Py 108 (C) excimer emission for SDS/Py = 108...

When pyrene was adsorbed onto silica gel from cyclohexane solution, the prominant excimer fluorescence band at 4650 A was no longer observed, but the monomer fluorescence band at 3900 A remained little changed.9 This inhibition of the excimer fluorescence indicates that the molecules are so strongly bound to the substrate surface that they become immobilized, thus preventing the conjugate n system overlap required to produce excimer emission. 

Fluorescence spectra and quantum yields of pyrene in supercritical CO2 have been determined systematically as functions of temperature, CO2 density, and pyrene concentration. Under near-critical conditions, contributions of the pyrene excimer emission in observed fluorescence spectra are abnormally large. The results cannot be explained in the context of the classical photophysical mechanism well established for pyrene in normal liquid solvents. The photophysical behavior of pyrene in a supercritical fluid is indeed unusual. The experimental results can be rationalized with a proposal that the local concentration of pyrene monomer in the vicinity of an excited pyrene molecule is higher than the bulk in a supercritical solvent environment. It is shown that the calculated ratios between the local and bulk concentrations deviate from unity more significantly under near-critical conditions (Sun and Bunker, 1995). 

A fourfold decrease in the IDIIM ratio was observed for the 5.3% peracetylated pyrenylmethyl polyethylenimine derivative in glycerol compared to methanol. The higher viscosity of the glycerol limits the mobility of the attached pyrene group necessary to form excimer, decreases the association rate, and hence lowers ID/IM. These samples at 77°C showed essentially no excimer emission. Clearly, diffusion of the pyrene moieties attached to the polymer side chains is necessary for excimer formation. 

Figure 6. Fluorescence quenching of pyrene by MV2+ in water, a) 1, b) 2. Monomer emission ( ), excimer emission ( ).

Farid and co-workers88 have investigated the effect of a glassy polymer host on the spectral position of the excimer emission peak produced by high concentrations of the compound methyl 4-(l-pyrenyl)-butyrate. The excimer peak position in a glassy polymer host was compared to the peak position in fluid solution for the following polymer hosts (and solvents) PS(toluene), PMMA(methyl isobutyrate), and poly-(vinyl benzoate) (methyl benzoate). The excimer emission peak of the pyrene compound in all three solvents occurred at about 20,800 cm-1, but the emission peak in all three polymer hosts was blue-shifted about 1900 cm-1 relative to the solution value. This is in contrast to the behavior of unsubstituted pyrene in PMMA 82) and PS 83), whose excimer peak does not shift from the solution value. 

Farid 88) did not report on the excimer lifetime of the pyrene compound in the systems that were studied. Nevertheless, they proposed that the blue shift of the excimer emission peak in glassy polymers relative to solution was due to improper orientation of the excimer components in the polymer matrix 88). This proposal is supported by the observation 88) that the blue shift of the excimer peak for the pyrene... 

In the pyrene system, the intermediate X has been identified with an excited dimer or excimer, since characteristic excimer emission is also observed. The process of triplet-triplet annihilation then consists of transfer of energy from one triplet to another to form excited dimeric species (S), which dissociates into an excited and a ground state singlets ... 

The influence of the nonuniform character of the interior of zeolites on the photophysics of adsorbed guest molecules has been observed. Pyrene molecules included in zeolite faujasites show both monomer and excimer emission [232,233]. As in the case of silica surfaces, the excitation spectra of the emission corresponding to the monomer and the excimer differ (Figure 36), suggesting that there are at least two independent sites, each responsible for monomer emission and excimer emission. Time-resolved emission studies of pyrene included in Na + -X and Na + -Y (<0.1 molecule per cage) indicate... 

Figure 36. Diffuse reflectance and excitation spectra of pyrene included in Na+X. Note the monomer and excimer emissions possess different excitation spectra. This difference may be the result of nonuniform distribution of pyrene molecules within cages.

Figure 4.22 The potential energy of excimer formation and emission of pyrene. The excimer ground state So is dissociative and association takes place only from the La excited state when the transition to Lb is forbidden. hvm is the molecular emission, and hve the excimer emission...

Figure 7.32 Kinetics of luminescence of pyrene following laser flash excitation. L, laser pulse profile M, monomer emission, E, excimer emission rise and decay. Horizontal axis, time in ns vertical axis, light intensity in arbitrary units. The three kinetic curves are normalized to a common maximum...

Examination of the spectra in Figure 13.10 shows that emission from the pyrene monomer has vibrational fine structure but that excimer emission is structureless. Structureless emission (or absorption) is characteristic of a transition to an unstable, dissociative state. Figure 13.11, in which potential energy is plotted against internuclear distance, shows why for a diatomic molecule. The lower state, being dissociative, has no vibrational fine structure and therefore emission to it is not quantized. 

Since Forster s original work, a large number of aromatic compounds, including benzene, naphthalene, and anthracene, have been found to have concentration-dependent fluorescence spectra under some conditions. Most of these excimers are not as stable a.s the pyrene prototype, and require lower temperatures or higher concentrations to be observed.29 Some crystals also exhibit excimer emission. Crystalline pyrene, for example, has only a single structureless fluorescence band of the same energy as its excimer emission in solution.30... 

We report on steady-state and time-resolved fluorescence of pyrene excimer emission in sub- and supercritical C02. Our experimental results show that, above a reduced density of 0.8, there is no evidence for ground-state (solute-solute) interactions. Below a reduced density of 0.8 there are pyrene solubility complications. The excimer formation process, analogous to normal liquids, only occurs for the excited-state pyrene. In addition, the excimer formation process is diffusion controlled. Thus, earlier reports on pyrene excimer emission at rather "dilute pyrene levels in supercritical fluids are simply a result of the increased diffusivity in the supercritical fluid media. There is not any anomalous solute-solute interaction beyond the diffusion-controlled limit in C02. 

Steady-State Experiments. Figure 3 shows a series of density-dependent steady-state emission spectra for 100 /zM pyrene in COj. The long wavelength, structureless excimer emission is clearly evidenced. (Again, at this concentration in a normal... 

Figure 8 shows a pair of typical time-resolved fluorescence decay traces for 100 / M pyrene in supercritical CO2 (Tr = 1.02 pr = 1.17). Note that the ordinate is logarithmic. The upper and lower panels show results for selective observation in the monomer (400 +. 10 nm) and excimer (460 + 10 nm) regions of the pyrene emission spectrum. Several interesting features are apparent from these traces. First, both decay processes are not single exponential. Second, the excimer emission has a significant contribution from a species that "grows in" between 30 - 75 ns this is a result of the excimer taking time to form (i.e., k in Figure 1). Third, the fits between the experimental data and the model shown in Figure 1 are good. Detailed analysis of these decay traces (10,11,21-26) yields the entire ensemble of photophysical kinetic parameters for the pyrene excimer in supercritical C02.

Figure 5. Ground state association of pyrene and pyrene "excimer" emission. Excitation and emission opectra of pyrene on silica gel ( excitation (observed at 390 nml...

Ueno et al. prepared y-CD derivatives with two pyrene moieties at AB, AC, AD, and AE glucose units (71,72,73, and 74, respectively) [71], The compounds show predominant excimer emission in aqueous 30% DMSO solution. The ex-cimer intensity slightly increases upon addition of ( )-bomeol for all of the hosts, whereas it decreases remarkably upon addition of lithocholic acid for AD and AE isomers. 

The (3-CD derivative bearing two pyrenes attached at one appending chain (75) was also prepared [72]. It exhibits both monomer and excimer emissions even though the excimer emission is remarkable in a 20% DMSO aqueous solution. This system is also responsive to guest compounds, and a remarkable decrease in the excimer emission was observed when lithocholic acid was added. 

Enhanced excimer emission was also observed from PBAC bound to a-ZrP [20], Excimer formation from pyrene is well known in aqueous solutions [54], As in the case with AMAC, excimer formation is increased with PBAC concentration (Fig. 16) due to increased local concentrations but with two significant differences. Hydrophobic interactions between the pyrene molecules favor the aggregation of PBAC even at moderate coverages and the PBAC singlet excited state is much longer lived ( 200 nsec) than that of AMAC ( 10 nsec) these factors, in turn, promote excimer formation even at low loadings. The broad, red-shifted fluorescence band with a peak centered around 470 nm, characteristic of the pyrene excimer emission, is evident in Fig. 16. Rapid formation of the excimer at low coverages is also evident from the plot of the ratio of emission intensities at... 

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