Porphyrin, Phthalocyanine and Porphyrazine Derivatives with Multifluorenyl Substituents as Efficient Deep-Red Emitters
writer：Carl A. Barker, Xianshun Zeng, Sylvia Bettington, Andrei S. Batsanov, Martin R. Bryce, and Andrew Be
keywords：Fluorine, fluorescence, phthalocyanines, porphyrazine, porphyrinoids
source：期刊
specific source：Chem. Eur. J. 2007, 13, 6710
Issue time：2007年
The synthesis and photophysical properties are described for a series of porphyrin, phthalocyanine and pyrazinoporphyrazine derivatives which bear four or eight peripheral fluorenyl substituents as antennae.Representative examples are 5,10,15,20-tetra(9,9-dihexyl-9H-fluoren-2-yl)porphyrin (2), 5,10,15,20-tetrakis[4-(9,9-dihexyl-9H-fluoren-2-yl)phenyl]porphyrin (3), 2,3,9,10,16,17,23,24-octakis(9,9-dihexyl-9H-fluoren-2-yl)-29H,31Hphthalocyanine (8) and 2,3,9,10,16,17,23,24-octakis[4-(9,9-dihexyl-9H-fluoren-2-yl)phenyl]-29H,31H-tetra-pyrazinoporphyrazine (9).Palladiummediated Suzuki–Miyaura cross-coupling reactions have been key steps for attaching the substituents.T he compounds are deep-red emitters: lmax(em)=659 (3), 737 (8) and 684 nm (9).T heir absorption and emission spectra, their fluorescence lifetimes and quantum yields are correlated with the structures of the macrocycles and the substituents.T he solution fluorescence quantum yields of porphyrin derivatives substituted with fluorene (2–4) and terphenyl substituents (7) (Ff=0.21–0.23) are approximately twice that of tetraphenylporphyrin.F or phthalocyanine derivative 8, Ff was very high (0.88). Specific excitation of the fluorine units of 8 produced emission from both of them (lmax=480 nm) and also from the phthalocyanine core (lmax=750 nm), indicating a competitive rate of energy transfer and radiative decay of the fluorenes.Organic light-emitting devices (OLEDs) were made by spincoating techniques by using a polyspirobifluorene (PSBF) copolymer as the host blended with 3 (5 wt.%) in the configuration ITO/PEDOT:PSS/PSBF copolymer:3/Ca/Al.Deep-red emission (lmax=663 nm; CIE coordinates x=0.70, y=0.27) was observed with an external quantum efficiency of 2.5% (photons/electron) (at 7.5 mAcm_2), a low turn-on voltage and high emission intensity (luminance) of 5500 cdm_2 (at 250 mA/m2).