Absorption and emission spectroscopic characterisation of a pyrene-flavin dyad

Abstract

The pyrene-flavin (isoalloxazine) dyad, PFD {C 44H 31N 5O 5; CA Index name: 1-pyrenepropanoic acid, α-[[4,10-dihydro-2,4-dioxo-10-phenylbenzo[g]pteridin-3(2H)-yl)acetyl]amino]-, phenylmethyl ester, (αR)–(9Cl); CA Registry number: 618907-57-6}, dissolved in either dichloromethane or acetonitrile is characterized by absorption and emission spectroscopy. Absorption cross-section spectra, stimulated emission cross-section spectra, fluorescence quantum distributions, quantum yields, and degrees of fluorescence polarisation are determined. The fluorescence decay after femtosecond pulse excitation is determined by fluorescence up-conversion. The ground-state absorption recovery is determined by picosecond pump and probe transmission measurements. The dye photo-stability is investigated by observation of absorption spectral changes due to prolonged blue-light excitation. The absorption spectrum of PFD dyad resembles the superposition of the absorption of isoalloxazine (flavin) and 1-methylpyrene. Long-wavelength photo-excitation of the flavin moiety causes fluorescence quenching by ground-state electron transfer from pyrene to isoalloxazine. Short-wavelength photo-excitation of the pyrene moiety causes (i) excited-state electron transfer from pyrene to isoalloxazine, and (ii) Förster-type energy transfer from pyrene to flavin followed by ground-state electron transfer from pyrene to flavin.