Chiral quinacridines react up to four times, step-by-step, with α-diazomalonates under Ru^II and Rh^II catalysis. By selecting the catalyst, [CpRu(CH₃CN)₃][PF₆] (Cp=cyclopentadienyl) or Rh₂(oct)₄, chemo and regioselective insertions of derived metal carbenes are achieved in favor of mono- or bis-functionalized malonate derivatives, respectively, (r.r.>49 : 1, up to 77 % yield, 12 examples). This multi-introduction of malonate groups is particularly useful to tune optical and chemical properties such as absorption, emission or Brønsted acidity but also cellular bioimaging. Density-functional theory further elucidates the origin of the carbene insertion selectivity and also showcases the importance of conformations in the optical response.