Diphenylanthracene, fluorescence

In such reactions the substantial heat of the simultaneous (concerted) formation of the carbonyl groups produced meets the energy requirement (8,16). In the reaction shown (8), the product is the highly fluorescent excited state of 9,10-diphenylanthracene [1499-10-1] (2). It is not necessary for the new carbonyl groups to be a part of the stmcture of the excited product, only that the excited state be formed synchronously with two carbonyl groups. 

Figure 7. Dependence of the fluorescence quamum yield of BMPC on solvent viscosity ( ) in linear alcohols, from methanol to dccanol, at 25°C, (o) in absolute ethanol between 200 and 298 K. The quantum yields were measured on optically thin samples (Am <0.2). The value in ethanol, 5.7x10, was determined relative to quinine sulfate in 0.5 mol 1" HjSO ((j)p=0.55 [62]) and 9,10-diphenylanthracene in cyclohexane (4ip=0.90 [63]). It was then used as a reference for the determinations in the other alcohols.

Similar results were obtained with the diperoxides 5 (R phenyl) and 5 a (R />-chlorophenyl) and dibenzanthrone or other fluorescers (perylene, rhodamine B, 9.10-diphenylanthracene, anthracene, fluorescein), with quantum yields of the respective chemiluminescence in the range 3.29 X 10 8.... 5.26 X 10 6. 

Another rather striking example demonstrates that the fluorescence efficiency of the respective dicarboxylates is not the most important factor in determining the chemiluminescence efficiencies of the hydrazides 9.10-diphenylanthracene-2.3-dicarbonic acid 25 has a fluorescence efficiency of about 0.9 (as has the parent compound 9.10-di-phenylanthracene) 94>. The corresponding hydrazide 26, however, gives a quantum yield of 48% that of luminol only (in DMSO/t-BuOK/ O2) 95) although 3-aminophtalic acid has a fluorescence efficiency of about 0.3 only. 

Gouanve et al. [9] presented another approach to designing copper nanosensors. They prepared cross-linked polystryrene beads (0 14 nm) and functionalized the surface with 1,4,8,11-tetraazacyclotetradecane (Cyclam), which selectively bound copper ions. The core of the beads was stained with a lipophilic fluorescent dye 9,10-diphenylanthracene by swelling. Fluorescence of the dye was quenched in the presence of Cu2+ due to FRET. The particles were suitable for sensing Cu2+ in micromolar concentrations. 

Figure 8.9. Time-resolved fluorescence spectra of 9,10-diphenylanthracene, recorded wi th time-correlated single photon counting, Aa = 360 nm. Parameters gate width and delay time relative to the intensity maximum of the excitation pulse.

Carbon disulfide quenches the fluorescence of anthracene quite efficiently,145,149 but seems to have little effect on its triplet lifetime.147 Diphenylanthracene in benzene fluoresces with a quantum yield of 0.8 and shows a high sensitivity to the oxygen concentration in photooxygenation reactions. With about 1 vol% of CS2 present, AC>2 is practically independent of [02] (> 10"5 mole/liter). In jjoth cases, where carbon disulfide was either used as solvent or was added to an otherwise strongly fluorescent solution, the quantum yields of photooxygenation followed... 

THF tetrahydrofuran, NaNap sodium naphthalenide, Na2St disodium stilbene dianion, BP benzoyl peroxide, DME 1,2-dimethoxyethane, TMBD tetramethylbenzidine dication diperchlorate, WBP Wurster s blue perchlorate, LP lauroyl peroxide, FLSPEC fluorescence spectrum obtained, FPSPEC fluorescence and phosphorescence spectrum obtained, FXSPEC fluorescence and eximer spectra obtained, DPAC12 9,10-dichlorO 9,10-dihydro-9,10-diphenylanthracene. 

In some molecules, the interaction can develop into a stronger force and the interplanar distance further reduced to form stable photodimers through covalent bonds. For example, anthracene forms a photodimer and no excimer emission is observed, whereas some of its derivatives with bulky substituents which hinder close approach give excimer fluorescence. In 9-methylanthracene both photodimer formation and excimer emission is observed. 9, 10-diphenylanthracene neither forms a photodimer nor emits excimer fluorescence due to steric hindrance. These observations are tabulated in the Table 6.3, which shows that the nature of the excited state is also important. 

Stevens401 irradiated anthracene, 9-phenylanthracene, and 9,10-diphenylanthracene at 3600 A and 280-300°C. He found that both 02 and NO quenched the fluorescence with similar efficiencies. For anthracene at 280°C and 9-phenylanthracene at 300°C, the ratios of the quenching rate constant for NO to the fluorescence rate constant are, respectively, 1120 and 1380 M 1. Ware and Cunningham4384 found the rate constant to be 1.97 x 1011 M 1 sec-1 for the quenching of anthracene vapor by NO at 280°C. They also found the anthracene-fluorescence constant to be 3.51 x 107 sec-1. The ratio of their two rate constants is 5500 M-1, about a factor of five larger than that found by Stevens. 

Anthracene undergoes a photochemical 9,10,9, 10 -cycloaddition which goes through the excimer as intermediate. Many aromatic molecules follow similar cycloaddition paths. The close approach of the molecules in the excimer is essential for bond formation, and steric hindrance can prevent the reaction unsubstituted anthracene dimerizes so fast that no excimer fluorescence can be detected, 9,10-dimethylanthracene shows both excimer fluorescence and photodimerization, but 9,10-diphenylanthracene shows neither excimer emission nor photodimerization (Figure 4.52). 

We studied electrochemically induced ET between a ferrocene derivative (FeCp-X) in single oil droplets and hexacyanoferrate(III) (Fe(III)) in the surrounding water phase the reaction system is schematically illustrated in Figure 11 [50,74], Tri-n-butyl phosphate (TBP) containing FeCp-X (ferrocene [X = H] or decamethylferrocene [X = DCM]), a fluorescent dye (perylene [Pe 0.5 mM] or 9,10-diphenylanthracene [DPA 10 mM]), and TBA+TPB (lOmM) is dispersed in an aqueous solution containing TBA+Cr, MgS04 (0.1 M), and potassium hexacyanoferrate(II) (Fe(II) 0.2 mM) with a 1 500 (oil/water) weight ratio as a sample emulsion. 

In organic ECL reactions, the luminescent species are generally derivatives of polyaromatic hydrocarbons where A and B in Eqs. (1) through (4) can be either the same species (leading to self-annihilation) or two different PAHs with either being the analyte (mixed system). Some examples of both self-annihilation and mixed system ECL reactions of organic molecules are listed in Tables 1 and 2. One well-studied example is the self-annihilation reaction between the anion and cation radicals of 9,10-diphenylanthracene (DPA) via an S-route in acetonitrile resulting in blue fluorescence characteristic of DPA [17] ... 

Bard etaL 5S6>5571 and Visco etaL 558) have quantitatively analyzed the intensity of pulsed ECL of 9,10-diphenylanthracene, tetraphenylpyrene and rubrene. By computer simulation of the electrode process and the subsequent chemical reactions the rates for chemical decay of the radical ions could be determined. Weaker ECL with fluorescence emission 559 or electrophosphorescence S60) occurs if the radical anion R - reacts with a dissimilar radical cation R,+ of insufficient high oxidation potential to gain enough energy for fluorescence emission, that is, if ht fluorescence) >23.06 (Ej >+. -Ej -.), e.g., in the annihilation of the anthracene radical anion with Wurster s blue. For these process the following schemes are assumed (Eq. (242) ) ... 

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