Friedländer reactions of 4‐aminoacridine‐3‐carbaldehyde with 1,3‐, 1,4‐di‐, and 1,3,5‐triacetylbenzenes afforded a series of corresponding (benzob‐1,10‐phenanthrolin‐2‐yl)benzenes as new N,N,C‐polydentates. Reaction with 1,2‐diacetylbenzene afforded 1,2‐di(benzob‐1,10‐phenanthrol‐2‐yl)benzene with unexpected benzob‐1,10‐phenanthroline and 3‐oxoindeno1,2‐bbenzoj‐1,10‐phenanthroline in a ratio of 1:1.2:1. Metal complex formation of the ligands was examined to provide two isomeric Ru complexes, a pentaaza‐coordinated (N5Cl) complex Ru(tpy)(3aH)Cl(PF6) and a hexacoordinated (N5C) complex Ru(tpy)(3a)(PF6) in a ratio of 1:4 with 71% overall yield, whereas 3b‐eH afforded complex mixtures upon reactions with Ru(tpy)Cl3. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:650–656, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20358