A simple procedure for the synthesis of cyclopentafused polycyclic aromatic hydrocarbons (CP-PAH) with Pd(PPh3)2Cl2 catalyst has been applied to the one-pot palladium(0)-catalyzed coupling of 9,10-dibromoanthracene (1) with 2-methyl-3-butyn-2-ol. Reactions carried out in refluxing benzene in the presence of CuSO4/Al2O3 yielded 9,10-dialkynylanthracene 2a, alkynyl aceanthrylene 2b, and 2,7-disubstituted cyclopent[hi]aceanthrylene 2c in 13%, 23%, and 19% purified yields, respectively, with total conversions of 80-90%. Sealed tube reactions without copper at 110 °C improved the yield of 2c up to >75%. Single-crystal X-ray analyses of 2a and 2c reveal a three-dimensional hydrogen bonding network, producing a unique crystal packing. The packing structure of 2b is dominated by π-π stacking interactions between two aceanthrylene molecules. CP-PAHs 2b and 2c have potentially interesting fullerene-like photophysics. While the UV-vis and fluorescence spectra of 2a (ΦF = 0.87) show the characteristic vibronic structure of anthracene, the UV-vis spectra of ruby-red aceanthrylene 2b and greenish-black cyclopent[hi]aceanthrylene 2c extend well into the visible range. Isomers 2b and 2c showed no detectable fluorescence emission. Unlike fullerenes, compounds 2b and 2c are poor singlet oxygen sensitizers with measured 1O2 quantum yields of 0.02 and 0.06, respectively. As expected from a simple Hückel analysis, 2c has relatively low two-electron reduction potentials as determined by cyclic voltammetry.
ASJC Scopus subject areas
- Colloid and Surface Chemistry