2026ApJ...996..108R

Interstellar detections of several cyano derivatives of large polycyclic aromatic hydrocarbons (PAHs) have now been achieved, enabled by accurate laboratory measurements of their microwave rotational spectra. These results highlight the continued promise of other N-containing unsaturated PAHs, such as aromatic imines, as candidates for future laboratory studies and astronomical searches. In this work, we present broadband spectroscopic measurements of 9-iminofluorene and benzophenone imine in the 6-18 GHz band. These measurements yield accurate rotational, centrifugal distortion, and ¹⁴N quadrupole coupling constants for both molecules. Using these experimentally-derived constants, we attempted a search for both molecules in the cold molecular cloud TMC-1 using observations from the Green Bank Telescope. Neither of these two ketimines was detected above the current noise level, establishing upper limits for their column densities of 5.1 × 10¹² cm^–2 for 9-iminofluorene and 1.3 × 10¹³ cm^–2 for benzophenone imine. We also attempted a search for phenylmethanimine (both E/Z isomers) as the simplest aromatic aldimine, but neither was detected in TMC-1. To provide insight into these nondetections, we propose and evaluate different formation pathways using respective potential energy surfaces as determined by high-precision quantum chemical calculations. The result suggests the presence of an entrance barrier to forming the intermediate species, potentially explaining the low abundance.