Naphthalimide-Dyes Bearing Phosphine and Phosphorylamide Moieties

Abstract

1,8-Naphthalimides (NIs) represent a class of organic dyes with interesting optical properties that has been extensively explored in the last decades in lighting devices, chemosensors, optical probes or medicinal chemistry. However, despite their remarkable potential, reports on organometallic dyes bearing NIs are scarce and virtually inexistent regarding palladium(II) complexes. Herein, we report the synthesis of NIs bearing phosphine and amine chelating moieties and the characterization of their optical properties both as single molecules and when complexed on Pd(II) ions. It is shown that the introduction of phosphine moieties in the naphthalimide core results in a marked increase in non-radiative processes, leading to a significant reduction of the emission efficiency and lifetime of these dyes, compared to amine-bearing counterparts. The complexation to Pd(II) sequesters the electronic contribution of chelating moieties, with complexes assuming an optical behavior similar to that of unsubstituted 1,8-naphthalimide. The complexation significantly increases the acidity of chelating secondary amines, giving rise to an unexpected intramolecular reaction that results in the formation of a novel 1,8-naphthalimide dye bearing a cyclic phosphorylamide moiety. The new dye exhibits good emission quantum yield, long fluorescence lifetime and sensitivity to basic media, evidencing potential for application in optical imaging and sensing scenarios.