The development of cyclometalated rhodium and iridium complexes from first-and second-generation naphthaldimine-based poly(propyleneimine) dendrimer scaffolds of the type, DAB-(NH2)(n) (where n = 4 or 8, DAB = diaminobutane) has been accomplished. Four metallodendrimers were synthesised, viz. (Cp*MCl)(4)G(n) (1-4), by first reacting DAB-(NH2)(n) with napththaldehyde and subsequently metallating the Schiff-base dendrimers with the dimers [Cp*MCl2](2) (where M = Rh or Ir). Related mononuclear complexes [Cp*MCl(L)] (L = naphthaldimine) (5-6) were obtained in a similar manner. The molecular structures of 5 and 6 have been determined by single-crystal X-ray diffraction analysis and the in vitro anticancer activities of 1-6 were evaluated against the A2780 and A2780cisR human ovarian carcinoma cell lines. (C) 2014 Elsevier B.V. All rights reserved.