Tetratopic Terpyridine Building Unit as a Precursor to Wheel-Like Metallo-Supramolecules

In an effort to construct molecules with distinct shapes and functions, the design and synthesis of multitopic ligands are often able to play an important role. Here, we report the synthesis of a novel tetratopic organic ligand LA, which can be viewed as a bis-tenon with successive angular orientations in space. The particular ligand has been treated with different tailored metal-organic ligands to afford new members of the molecular wheel family (multi-rhomboidal-shaped wheel and bis-trapezium-shaped wheel) that show enhanced stability. Two-dimensional (2D) diffusion nuclear magnetic resonance (NMR) spectroscopy (DOSY), electrospray ionization (ESI) mass spectrometry, traveling wave ion mobility (TWIM), and gradient tandem mass spectrometry (gMS₂) experiments, as well as molecular modeling, have been employed to provide structural information and differentiate the isomeric separation process. In addition, considering that LA has rotational properties, it is expected to open the door to functional supramolecules and stimuli-responsive materials.