[n]Cycloparaphenylenes (n = 8-13, CPPs) were synthesized, and their physical properties were systematically investigated. [8] and [12]CPPs were selectively prepared from the reaction of 4,4'-bis(trimethylstannyl)biphenyl and 4,4''-bis(trimethylstannyl)terphenyl, respectively, with Pt(cod)Cl(2) (cod = 1,5-cyclooctadiene) through square-shaped tetranuclear platinum intermediates. A mixture of [8]-[13]CPPs was prepared in good combined yields by mixing biphenyl and terphenyl precursors with platinum sources. Products were easily separated and purified by using gel permeation chromatography. In (1)H NMR spectra, the proton of the CPPs shifts to a lower field as n increased due to an anisotropic effect from the nearby PP moieties. Although the UV-vis spectra were rather insensitive to the size of the CPPs, the fluorescence spectra changed significantly in relation to their size. A larger Stokes shift was observed for the smaller CPPs. Redox properties of the CPPs were measured for the first time by using cyclic voltammetry, and the smaller CPPs had lower oxidation potentials. The results are consistent with the HOMO energies of CPPs, of which the smaller CPPs had higher energies.

We report the synthesis and characterization of perfluoropentacene as an n-type semiconductor for organic field-effect transistors (OFETs). Perfluoropentacene is a planar and crystalline material that adopts a herringbone structure as observed for pentacene. OFETs with perfluoropentacene were constructed using top-contact geometry, and an electron mobility of 0.11 cm2 V-1 s-1 was observed. Bipolar OFETs with perfluoropentacene and pentacene function at both negative and positive gate voltages. The improved p-n junctions are probably due to the similar d-spacings of both acenes. Complementary inverter circuits were fabricated, and the transfer characteristics exhibit a sharp inversion of the output signal with a high-voltage gain.

One of the keys to highly efficient phosphorescent emission in organic light-emitting devices is to confine triplet excitons generated within the emitting layer. We employ “starburst” perfluorinated phenylenes (C60F42) as a both hole- and exciton-block layer, and a hole-transport material 4,4′,4″-tri(N-carbazolyl) triphenylamine as a host for the phosphorescent dopant dye in the emitting layer. A maximum external quantum efficiency reaches to 19.2%, and keeps over 15% even at high current densities of 10–20 mA/cm2, providing several times the brightness of fluorescent tubes for lighting. The onset voltage of the electroluminescence is as low as 2.4 V and the peak power efficiency is 70–72 lm/W, promising for low-power display devices.

The interfaces formed between pentacene (PEN) and perfluoropentacene (PFP) molecules and Cu(111) were studied using photoelectron spectroscopy, X-ray standing wave (XSW), and scanning tunneling microscopy measurements, in conjunction with theoretical modeling. The average carbon bonding distances for PEN and PFP differ strongly, that is, 2.34 A for PEN versus 2.98 A for PFP. An adsorption-induced nonplanar conformation of PFP is suggested by XSW (F atoms 0.1 A above the carbon plane), which causes an intramolecular dipole of approximately 0.5 D. These observations explain why the hole injection barriers at both molecule/metal interfaces are comparable (1.10 eV for PEN and 1.35 eV for PFP) whereas the molecular ionization energies differ significantly (5.00 eV for PEN and 5.85 eV for PFP). Our results show that the hypothesis of charge injection barrier tuning at organic/metal interfaces by adjusting the ionization energy of molecules is not always readily applicable.