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(CH 3 CN) 3 ][PF 6 ] (Cp = cyclopentadienyl) or Rh 2 -(oct) 4 , chemo and regioselective insertions of derived metal carbenes are achieved in favor of mono-or bisfunctionalized malonate derivatives, respectively, (r.r. > 49 : 1, up to 77 % yield, 12 examples). This multiintroduction 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.

Supporting information (SI) for this article is given via a link at the end of the document. It contains experimental conditions, full characterizations of all new compounds (PDF); CSP-HPLC traces, pKa determination, UV-Vis, ECD, CPL and fluorescence spectra; computational details. In addition, the dataset for this article can be found at the following