|標題:||Electrogenerated chemiluminescence of a spirobifluorene-linked bisanthracene: A possible simultaneous, two-electron transfer|
|作者:||Sartin, Matthew M.|
Bard, Allen J.
Department of Applied Chemistry
Department of Computer Science
|摘要:||We report the electrogenerated Chemiluminescence (ECL) of 2,2'-bis(10-phenylanthracen-9-yl)-9,9'-spirobifluorene (spiro-FPA), a dichromophoric molecule composed of two phenylanthracenes linked by a spirobifluorene moiety (PA similar to X similar to PA). The results are compared to those for 9,10-diphenylanthracene (DPA), a related molecule with a single chromophore. Cyclic voltammetry (CV) of spiro-FPA shows two reversible, closely spaced, one-electron transfers on both reduction and oxidation, occurring at E-1,E-red degrees = -2.02, E-2red degrees = -2.07 V vs SCE and E-1,E-OX degrees = 1.14, E-2,E-OX degrees = 1.20 V vs SCE. The potentials for each pair are close enough to appear as a single peak in CV, indicating that the spirobifluorene moiety interrupts conjugation between the redox centers. The potentials observed are similar to those of DPA, which shows E-red degrees = -2.06 V vs SCE and E-OX degrees = 1.15 V vs SCE. The absorbance spectrum of spiro-FPA shows lambda(max,abs) 377 nm, with epsilon(377) = 25 700 M-1 s(-1), while DPA exhibited lambda(max,abs) = 374 nm, with epsilon(374) = 13 800 M-1 s(-1), demonstrating that spiro-FPA has twice the available chromophores as DPA. Photoluminescence (PL) data for spiro-FPA shows lambda(max,PL) = 434 nm, with Phi(PL) = 0.74, while DPA fluoresces at 420 nm with Phi(PL) 0.91; thus, there is greater solvent or structural relaxation in the spiro-FPA excited state, which may account for the greater internal conversion. Unlike DPA, the ECL spectrum of spiro-FPA exhibits long-wavelength emission not observed in the PL. We attribute this emission to excimers formed during annihilation ECL. Steric hindrance prevents DPA from forming excimers, even in ECL, but spiro-FPA annihilation can occur between pairs of di-ions (PA(center dot-)similar to X similar to PA(center dot-) and PA(center dot+)similar to X similar to PA(center dot+)), which are electrostatically more strongly attracted to one another than the mono-ions. This greater electrostatic attraction may be sufficient to overcome the steric hindrance to excimer formation. Lowering the electrolyte concentration decreases the electrostatic shielding of the ions from one another; thus, the increase in longer wavelength ECL accompanying a decrease in electrolyte concentration supports the role of the di-ions in excimer formation. Additionally, simulations show, consistent with experiment, a more rapid decrease in excimer concentration than in excited monomer concentration as a function of time after each potential pulse. This is probably due to the greater number of scavenging reactions available for di-ions. The simulations are confirmed experimentally when lower potential pulsing frequencies yield lower relative excimer emission. Since an excited state created by one-electron transfer between two di-ions should be rapidly quenched via electron transfer by the other PA moiety, the existence of excimers suggests the possibility of simultaneous, two-electron transfer to generate the excimer.|
|期刊:||JOURNAL OF THE AMERICAN CHEMICAL SOCIETY|