Boron nitrogen doping of polyaromatic hydrocarbons (PAH), such as borazine-core hexabenzocoronene, presents possibilities for tuning the properties of organic electronics and nanographene materials while preserving structural characteristics of pure hydrocarbons. Previous photochemical studies have demonstrated extension of a borazine-core PAH network (1,2:3,4:5,6-tris(o,o'-biphenylylene)borazine, 1) by photo induced cyclodehydrogenation. We present steady-state and femtosecond-to-microsecond resolved spectroscopic studies of the photophysics of 1 and a related borazine-core PAH in order to characterize competing excited state relaxation pathways that determine the efficacy of bond formation by photocyclization. Transient spectra evolve on time scales consistent with S-1 fluorescence lifetimes (1-3 ns) to features that persist onto microsecond time scales. Nanosecond-resolved oxygen-quenching measurements reveal that long-lived metastable states are triplets rather than cyclized products. Determination of fluorescence and triplet quantum yields reveal that photochemical bond formation is a minor channel in the relaxation of 1 (similar to 5% or less), whereas highly efficient fluorescence and intersystem crossing result in negligible photoinduced bond formation in more extended borazine-core networks. Results of computational investigations at the RICC2 level reveal sizable barriers to cyclization on the S-1 potential energy surfaces consistent with quantum yields deduced from experiment. Together these barriers and competing photophysical pathways limit the efficiency of photochemical synthesis of BN-doped polyaromatics.