Electrochemistry and electrogenerated chemiluminescence of a novel donor-acceptor FPhSPFN red fluorophore

Mei Shen, Joaquín Rodríguez-López, Yi Ting Lee, Chin Ti Chen, Fu Ren F. Fan, Allen J. Bard

Research output: Contribution to journalArticlepeer-review

Abstract

We report here the electrogenerated chemiluminescence (ECL) of a red fluorophore diphenylaminospirobifluorenylfumaronitrile (FPhSPFN). FPhSPFN contains two diphenylamino groups as strong electron donors at the ends linked through a nonplanar bulky spirobifluorene linker to a common fumaronitrile group as a strong electron acceptor. The cyclic voltammetry of this compound shows two one-electron transfer reduction waves and one single overall two-electron oxidation wave consisting of closely spaced waves with a peak separation of 63 mV. Chronoamperometry with an ultramicroelectrode (UME) confirmed that each reduction wave involves a 1e transfer and that the oxidation wave contains an overall 2e transfer. The first reduction wave is Nernstian, Eo 1,red =-1.09 V versus SCE, and the second reduction wave, E o2,red =-1.50 V versus SCE, produces a film on the electrode. By comparison to a digital simulation, the oxidation is assigned to two reversible, closely spaced, one-electron processes for oxidation with E o1,ox = 1.05 V and Eo2,ox = 1.11 V versus SCE. A large wavelength shift (∼35 nm) was observed in ECL as compared to photoluminescence (PL). The ECL spectrum showed a maximum emission at 708 nm with a red-shifted shoulder at around 750 nm. ECL was studied in mixtures of benzene/acetonitrile at different composition ratios; an increase in the ratio of the ECL intensity of the shoulder with respect to the main peak emission was observed with increasing solvent polarity. ECL generated with BPO as a coreactant also showed the red-shifted shoulder at the same ratio as that with annihilation.

Original languageEnglish (US)
Pages (from-to)9772-9780
Number of pages9
JournalJournal of Physical Chemistry C
Volume114
Issue number21
DOIs
StatePublished - Jun 3 2010
Externally publishedYes

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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