Synthesis, characterization, and heparin-binding study of a self-assembled p-cymene-Ru(ii) metallocycle based on a 4-amino-1,8-naphthalimide Tröger's base supramolecular scaffold

Abstract

We report the very first example of a self-assembled p-cymene-Ru(II) metallocycle based on a green emitting 4-amino-1,8-naphthalimide Tröger's base (TBNap) supramolecular scaffold. A new cleft-shaped TBNap-derived di-4-picolyl donor was synthesized and reacted in a 2 : 2 stoichiometry ratio with a dinuclear Ru(II) acceptor (Ru-A) to generate a [2 + 2] self-assembled metallocycle (TBNap-Ru-MC) in good yield. Both TBNap and TBNap-Ru-MC showed positive solvatochromism in different solvents with varying polarities. In addition, the binding propensity of cationic TBNap-Ru-MC toward the heparin polyanion was determined using fluorescence titration studies. The initial fluorescence emission of TBNap-Ru-MC was quenched upon the gradual addition of the heparin polyanion, and the Stern–Volmer quenching constant (K_SV) was calculated to be 3.97 × 10⁵ M⁻¹.