Three fluorinated BsubPcs have been synthesized and characterized. Crystals suitable for XRD were grown by slow vapor diffusion and sublimation. Analysis of their crystal structures revealed a dimeric association of BsubPc units for F 5 BsubPc and columnar packing for F 12 BsubPc and F 17 BsubPc. Cyclic volatmmetry (CV) was used to probe the frontier orbital energy levels of these compounds in both dichloromethane and acetonitrile solution; however, only F 5 BsubPc underwent oxidative events, whereas all three compounds underwent reductive events. A -362 and -37 mV shift in the reductive peak potential was observed for peripheral and axial fluorination, respectively, as measured by cyclic voltammetry. Solution UV-vis absorption and photoluminescence spectra were measured in dichloromethane. All three compounds demonstrated air-stable n-type conductivity in single-carrier devices and extremely narrow orange EL emission with a fwhm of only ∼30 nm. F 5 BsubPc showed a maximum luminescence of 122 cd/m 2 at 8 V, with a maximum current efficiency of 0.03 cd/A, whereas the devices fabricated from F 12 BsubPc and F 17 BsubPc produced luminescence with a maximum value of <1 cd/m 2 .

In the title compound, C31H7BF12N6O, mol­ecules are arranged into one-dimensional columns with an inter­molecular B⋯B distance of 5.3176 (8) Å. Bowl-shaped mol­ecules are arranged within the columns in a concave bowl-to-ligand arrangement separated by a ring centroid distance of 3.532 (2) Å between the benzene ring of the 4-methyl­phen­oxy ligand and one of the three five-membered rings of a symmetry-related mol­ecule.

The title compound, C24BBrF12N6 or Br-F12BsubPc (BsubPc is boronsubphtalocyanine), has a bowl-shaped structure with an approximate mol­ecular C 3v symmetry characteristic of boronsubphthalocyanine compounds. In the crystal, mol­ecules are arranged in one-dimensional columns and the boron–subphthalocyanine units within each column are offset and angled in a bowl-to-ligand packing arrangement such that the axial Br atom rests in the aromatic concaved bowl of the neighboring subphthalocyanine with an inter­molecular Br⋯B distance of 3.721 (3) Å.